JP2009242797A - Norbornene polymer, its composition, and lithography method using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide non-self developing type and developing type norbornene polymers applicable to a liquid-immersion lithography process, a manufacturing methods for the polymers, a composition using the polymer, and the liquid-immersion lithography process using the composition. <P>SOLUTION: The non-self developing type and developing type norbornene polymers useful for the liquid-immersion lithography process, the method for manufacturing such polymers, the composition using such a polymer, and the liquid-immersion lithography process using such a composition, are provided. In more details, there are provided: a norbornene polymer which is useful to form a developing layer and a topcoat layer to cover the developing layer in the liquid-immersion lithography process; and its process. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

(priority)
This application is filed on US Provisional Application Nos. 60/655351 and 60 entitled “Norbornene-Based Polymers and Lithographic Methods Using Norbornene-Based Polymers” filed on February 23, 2005 and October 21, 2005, respectively. No. 729091 and US provisional entitled “Protective Film Forming Material and Photoresist Pattern Forming Method Using It” filed on February 25, 2005, July 7, 2005 and October 21, 2005, respectively. Claims priority based on application Nos. 60/65501, 60/687871 and 60/728756, the entire provisional patent application identified above is hereby incorporated by reference in its entirety. To do.

(Technical field)
Embodiments according to the present invention generally relate to norbornene-based polymers, methods of making the polymers, compositions using the polymers, and lithographic methods using the compositions; more particularly, such embodiments include , Norbornene-based polymers useful for the formation of compositions containing said polymers and compositions so formed, such compositions being non-developable protective layers, developable layers and combinations thereof For forming a layer useful in an immersion lithography method as well as in an immersion lithography method using such a composition.

(background)
Traditionally, methods for achieving smaller shapes have been to select a lithographic source having a shorter wavelength, increase the numerical aperture (NA) of the lens of the lithography system, or a combination thereof. While these methods have been successful, it has become increasingly difficult to overcome the problems associated with utilizing such changes for each wavelength reduction and / or NA increase.

  In recent years, it has been suggested that rather than selecting a new lithography source with a shorter wavelength, eg, 157 nm, the resolution of the current standard source of 193 nm can be extended by the use of immersion lithography. Such an immersion lithography process replaces the usual “air gap” between the final lens of the lithography tool and the exposed substrate with a fluid such as water. Water has a much higher index of refraction than air, allowing lenses with NAs greater than 1 to be used without causing the depth of focus (DOF) reduction that would otherwise occur. Therefore, it is considered that a minimum shape of 45 nm or less can be achieved by such an approach.

  However, there are new problems that need to be solved to successfully perform immersion lithography for microelectronic device manufacturing. For example, typically, a substrate that is exposed during a microlithography process is repeatedly repositioned relative to the lithography tool lens to fully expose all positions on the substrate. The presence of immersion fluid (also referred to herein as “immersion medium” or “IM”) results in fluid residue due to this movement, and such residue increases the potential for such processes to be unacceptable. There is a concern that this will result. Also, with respect to fluid residues or residues, any proposed solution to this problem will reduce the number of substrates per hour that the lithography tool can sufficiently expose if the moving speed (scanning capability) decreases. It must be taken into account that such movement must not significantly reduce the speed currently achieved, as it may result in an unacceptable reduction.

  In addition to problems with IM residue and scan capability, the use of IM raises concerns about problems that can arise from fluids in direct contact with the photoresist layer that can reduce the resolution of the layer. For example, such problems include, in particular: 1) leaching of small molecules such as photoacid generators (PAGs) and PAG photolysis products from photoresist films into IM, and 2) immersion media or components thereof. Absorption into the photoresist film.

  One method that has been investigated to eliminate or reduce these and other problems associated with immersion lithography is the use of an intervening layer disposed overlying a photoresist film. Such an intervening layer, also referred to as a “topcoat” or “protective layer”, is therefore arranged to accept the immersion material and prevent or greatly reduce any effects relating to the technical problems 1 and 2 described above. With respect to scanning capability, the use of a topcoat allows the design of materials with specific properties that eliminate or greatly reduce the possibility of IM residue with little or no reduction in tool movement speed.

  In recent years, several materials have been proposed for use as topcoat layers, including fluoropolymers. Such materials have been shown to have a positive effect on the problems discussed above, but it is necessary to use a solvent for their removal. Any topcoat layer must be removed so that it can be developed into an underlying photoresist layer, so for materials that require the use of a special solvent to remove it, such removal is an extra step. There is a problem in that it adds undesired equipment and material costs, as well as costs associated with the reduced productivity caused by the extra steps.

  It is therefore desirable to provide a solution that can be implemented immediately, for example a solution to the above mentioned technical problems that may arise in the case of immersion lithography. Such a solution provides for the reduction or prevention of leaching of small molecule photoresist layers into the immersion medium and also reduces or prevents the absorption of such immersion medium into such layers. There must be. Such a solution should also help reduce deficiencies from the level found when immersion lithography is performed without the use of such a solution. Furthermore, such a solution is cost effective and requires a significant alternative process as observed in the case of the solvent-removable topcoat materials described above without significantly reducing the scanning capability in use. It is desirable that the scanning capability is not significantly reduced when used.

(Detailed description)
The embodiment according to the present invention aims to solve the above-mentioned technical problems of immersion lithography. Such embodiments include polymeric materials, methods for making such materials, compositions of such materials useful for the formation of both developable and non-developable films, and immersion using such films. Includes lithography methods. Such embodiments reduce or eliminate leaching of small molecules from the development layer or film into the immersion medium, absorption of such media or components of such media into the development layer, and scanning capabilities. This reduces or eliminates the deficiencies due to any non-retaining immersion fluid formed during exposure of such a developer layer throughout the substrate without significant impact on the substrate. Where such an embodiment includes a topcoat or non-developable layer, it provides a layer that is soluble in an aqueous base, thus eliminating the need for a separate topcoat removal step using a solvent.

The polymeric material of embodiments of the present invention comprises polycyclic repeating units. Such polycyclic repeating units, when referred to as “norbornene type”, are as follows: X is —CH ₂ —, —CH ₂ CH ₂ —, O or S, and n is 0 Units derived from substituted or unsubstituted norbornene-type monomers that are integers of -5:

  The term “non-self imageable polymer” refers to direct irradiation, such as 193 nanometers (nm) or 157 nm when formed into a film or layer having an essentially uniform thickness on a substrate. It means a polymer (or resin) that is not developable upon irradiation with a radiation source.

  The terms “topcoat material” or “topcoat composition” are used interchangeably herein and refer to a material or composition that includes a non-self-developing polymer. Such a composition is useful for forming a protective film over the photoresist layer to protect the photoresist layer during an immersion lithography process. The protective film (or topcoat layer) is a non-self-developing film.

  The term “imageable polymer” means that when formed into a film or layer having an essentially uniform thickness on a substrate, it can also be directly irradiated, for example by irradiation from a 193 nm or 157 nm source. Means a polymer (also referred to as a resin) that can be developed via

  The terms “developable material”, “developing composition” or “photoresist material” are used interchangeably herein and refer to a substance or composition comprising a developable polymer. Such a composition is useful for forming a patternable development layer (or photoresist layer). The photoresist materials of the present invention are useful in immersion and non-immersion lithography processes.

  The terms “immersion material”, “immersion medium” and “immersion fluid” are used interchangeably herein to refer to the air in the exposure radiation path between the lens and substrate used for focusing and orientation of the radiation. Means the fluid used to replace. As shown in FIG. 1, the fluid has a refractive index that is greater than air and lower than any layer disposed between the lithography tool lens and the substrate top surface.

  The terms “non-retained immersion material”, “non-retained immersion medium” and “non-retained immersion medium” are used interchangeably herein and are located between the lithography tool lens and the top surface of the substrate as shown in FIG. Means the part of the immersion material spaced from the immersed medium. In addition to this definition, the terms “scan ability” and “scan speed endurance” are used interchangeably herein and refer to the relative speed at which the substrate moves relative to the lens. In the presence of immersion media, scanning capability measurements include whether any non-retained immersion material has been formed. By way of example, in an immersion lithography process, high scanning capability means that little or no unretained immersion material is observed at an acceptable speed movement of the lithography tool.

  “Contact angle”, “sliding angle” and “backward angle” mean angles as specified in FIG. Furthermore, the term “rolling angle” is used herein synonymously with “falling angle”.

(polymer)
Some embodiments according to the present invention include non-self-developed norbornene-based polymers having recurring units of some or all of formulas I, II, III and IV shown below. Some embodiments include compositions that use such polymers to form a topcoat or protective layer on a pre-formed photoresist layer. The polymer is non-developing and the topcoat layer formed therefrom is also non-self-developing.

  The topcoat layer is for receiving an immersion fluid (or medium) and protects or separates the photoresist or developer layer from the immersion fluid, allowing an immersion photolithography process. That is, the photoresist layer is physically removed (separated) from direct contact with the immersion fluid due to the presence of the topcoat layer therebetween. In this way, some or all of the technical problems described above can be eliminated or avoided, or advantageously at least their effects can be reduced. In addition to these problems, embodiments of the topcoat layer of the present invention are advantageously characterized by exhibiting a high contact angle with aqueous fluids and thus are hydrophobic. Such hydrophobicity is believed to be a desirable property to minimize any chemical or other interaction between the material and the aqueous immersion fluid that contacts it. Still further, such topcoat embodiments exhibit high receding angles and low tumbling angles (see FIG. 2), which is also indicative of the high hydrophobicity of such materials, and thus immersion lithography. It is believed that this is an indicator of how the embodiment functions dynamically during its use as a topcoat or protective layer for the process. Thus, when topcoat layers that exhibit high contact and receding angles and low tumbling angles are used during the immersion lithography process compared to other materials, failures due to non-retentive immersion fluids are rare over a wide range of scan speeds. Or it was found that it was not observed at all. That is, such an embodiment has excellent scanning capabilities.

  Some other embodiments according to the invention include developable norbornene-based polymers having recurring units represented by some or all of formulas I, II, III, IV, V and VI shown below. . Some embodiments include compositions that use such polymers, which are disposed on a substrate to form a development layer or film thereon. Such compositions for forming a development layer are also referred to as photoresist compositions or materials and layers forming a photoresist layer or film.

  In some development layer embodiments according to the present invention, such a layer can directly receive an immersion fluid (or medium) to enable an immersion photolithography process. In other embodiments, such a photoresist composition is used to form a developer layer that receives a topcoat composition for forming a topcoat layer thereon.

  Preferably, some embodiments of the photoresist composition according to the invention advantageously provide a developing layer characterized by exhibiting a high contact angle with an aqueous fluid and thus being hydrophobic. Such hydrophobicity is believed to be a desirable property to minimize any chemical or other interaction between the material and the aqueous immersion fluid that contacts it. Still further, such development layer embodiments also exhibit high receding angles and low tumbling angles (see FIG. 2), which are indicative of the high hydrophobicity of such materials, and thus It is believed that it is an indication of how the embodiment will function dynamically during use in an immersion lithography process. Thus, when a developer layer that exhibits high contact and receding angles and low tumbling angles compared to other materials is used during the immersion lithography process, a topcoat layer may be formed thereon. If not, the failure due to the non-retaining immersion fluid occurs little or no over a wide range of scanning speeds. That is, such an embodiment has excellent or high scanning capability.

In some embodiments according to the present invention, Formula I:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a QNHSO ₂ R ⁵ group (where Q is 1 to 5). A linear or branched alkyl spacer of carbon, and R ⁵ is a perhalo group of 1 to about 10 carbon atoms)]
A non-self-developing polymer comprising at least one repeating unit represented by is provided.

In some embodiments according to the invention, the other R ¹ to R ⁴ that are not QNHSO ₂ R ⁵ groups are each independently hydrogen; a linear or branched alkyl or haloalkyl group, such as 1 to about 20 Of polymers of formula I, in one embodiment from 1 to about 12 carbon atoms, and in other embodiments from 1 to about 4 carbon atoms.

In some embodiments, Q is a 1 to 3 carbon linear alkyl spacer and R ⁵ contains 1 to 4 carbon atoms. In other embodiments, Q and R ⁵ are each independently 1 or 2 carbon atoms, and in yet other embodiments, each is 1 carbon atom. Typically, the halogen of R ⁵ is selected from F, Br or I. In an exemplary embodiment of the invention, X is —CH ₂ —, ^one of R ¹ to R ⁴ is a QNHSO ₂ R ⁵ group, the other is hydrogen, n is 0, and Q is —CH ₂ —. , R ⁵ is —CF ₃ —. The repeating unit of formula I generally imparts aqueous alkaline solubility to the polymer.

In some embodiments according to the present invention, the non-self-developed polymer has the formula II:
[Wherein X and n are as defined for formula I and R ⁶ to R ⁹ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group, wherein at least one of R ⁶ to R ⁹ is a -Q ^‡ (CO) O- (CH ₂ ) _m -R ¹⁰ group (where Q ^‡ is optional and, if present) A linear or branched alkyl spacer of 1 to 5 carbons, m is an integer of 0 or 1-3; R ¹⁰ is a linear or branched perhaloalkyl of 1 to 10 carbon atoms. Is)]
A second type of repeating unit represented by

In some embodiments, Q ^‡ is absent or is a linear alkyl spacer of 1 to 3 carbons and R ¹⁰ has 1 to 4 carbon atoms. In other embodiments, Q ^‡ is absent or is 1 carbon atom, R ¹⁰ has 1 or 2 carbon atoms, and in a further embodiment R ¹⁰ has 1 carbon atom. Typically, the halogen of R ¹⁰ is selected from F, Br or I. In an exemplary embodiment of the invention comprising recurring units of the formula II, X is —CH ₂ — and one of R ⁶ to R ⁹ is —Q ^‡ (CO) O— (CH ₂ ) _m -R ¹⁰ groups, the others are each hydrogen, n is 0, m is 1, Q ^‡ is absent, and R ¹⁰ is -C ₂ F ₅ . The repeat unit according to Formula II is generally for providing hydrophobic control to the polymer and is generally used with other repeat units as defined herein to provide such hydrophobic control. That is, the more such repeating units are incorporated into the polymer, the more generally the hydrophobicity of the polymer increases.

In some embodiments according to the present invention, the non-self-developing polymer has the following formula III:
[Wherein X and n are as defined for formula I and R ¹¹ to R ¹⁴ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹¹ to R ¹⁴ is represented by the following formula:
(Wherein m is an integer from 1 to 3, Q ^‡ is as defined for Formula II, and Q ^* is a 1-5 carbon linear or branched alkyl spacer. )
Is one of the A, B or C groups of
It contains a repeating unit of the type represented by

In some embodiments comprising an A or C group, Q ^‡ is absent or is a 1 to 3 carbon linear alkyl spacer, and in the C group, Q ^* is a 3 or 4 linear chain. Or branched spacers. In other such embodiments, Q ^‡ is absent or is one carbon atom. In other embodiments comprising a B group, m is 1 or 2. In an exemplary embodiment of the invention comprising recurring units of the formula III, X is —CH ₂ —, one of R ¹¹ to R ¹⁴ is a B group and the others are each hydrogen, n is 0 and m is 1. The repeat unit of formula III is generally for imparting aqueous alkali solubility to the polymer and is generally used with other repeat units as defined herein to provide such aqueous alkali solubility.

In yet another embodiment of the invention, the non-self-developed polymer is of formula IV:
[Wherein X and n are those described in Formula I, and R ¹⁵ to R ¹⁸ are each independently hydrogen, a linear or branched alkyl group, or linear or branched. Wherein at least one of R ¹⁵ to R ¹⁸ is represented by the following formula:
(Wherein X is independently F or H, q is each independently an integer of 1 to 3, p is an integer of 1 to 5, and Q ^* is defined for Formula III) Z is a linear or branched halo or perhalo spacer of 2-10 carbons)
One of the D, E or F groups of
Still other types of repeating units represented by

In some embodiments comprising a D group, Q ^* is one carbon, X is F, q is 2 or 3, and p is 2. In some embodiments comprising an E group, Q ^* is one carbon and Z is a branched fluorinated alkyl chain of up to 9 carbon units. In some embodiments involving F groups, Q ^* is one carbon and q is 1 or 2. The repeat unit of formula IV is generally for providing hydrophobic control to the polymer in the same manner as described for the repeat unit of type II.

  Embodiments of the topcoat polymer of the present invention include repeat units represented by Formula I and repeat units such as, but not limited to, those represented by one or more of Formulas II, III and / or IV It should be understood to include polymers with other types of repeating units, including Further, certain embodiments of the invention include repeat units that do not fall within the scope and spirit of such formulas. For example, some embodiments include linear or branched alkyl substituted repeat units such as those derived from hexyl- or butyl-norbornene. Yet another embodiment comprises repeating units derived from linear or branched alkyl ester norbornene, such as isobornyl ester norbornene. These alternating repeating units can be substituted for or added to any of the above-described repeating units of formula II, III or IV.

  Where embodiments according to the invention comprise non-self-developed polymers having more than one distinct type of repeating unit represented by one or more of formulas I, II, III and / or IV, such repeats The molar ratio of units is (1): when the repeating unit (1) is represented by formula I and the others of (2) to (m) are independently represented by formula II, III or IV. 2) :. . . : (M) is approximately (30-99): (5-50):. . . (5-50), where m is an integer representing the last type of repeating unit to be distinguished and is generally 4 or less. In other such embodiments, such molar ratio is about (50-80) :( 5-30):. . . : (5-30). Of course, it is understood that for such a ratio, the sum cannot exceed 100. Where an embodiment comprises a repeating unit of the type of formula I and a repeating unit of the type represented by one of formulas II, III or IV, the mole percent (mol%) of the repeating unit of the formula I type is Generally between 40 and 99 mole percent, a sufficient amount of one or more other types of repeating units is provided to be 100 mole percent polymer. In embodiments of the topcoat polymer of the present invention having only repeating units of the type of formulas I and II, the type of formula I can generally range from 40 to 99 mol%, and in some embodiments, 60 to 90 mol%. In other exemplary embodiments, eg, polymers having repeat units of the type represented by one or both of formulas III and IV, in addition to the types represented by formulas I and / or II, the type of formula I The mole percent of repeat units is typically from about 40 to about 98 mole percent, the type of formula II (if present) is from about 1 to about 20 mole percent, and repeat units of the formula III and IV types Each independently is from about 1 to about 40 mole percent, if present. Of course, it should be understood that other polymer compositions having more or less of any particular type of repeating unit are also considered to fall within the scope and spirit of the invention. As discussed more fully below, the final preparation of the topcoat polymer is the result of certain design choices governed by the manner in which the topcoat layer formed from such a polymer is used.

  Furthermore, it should be noted that the specific amount of any specific repeating unit present in the polymer is the result of the “polymer design” process. That is, the physical and chemical properties of the repeating unit are often determined by forming the homopolymer, and such physical and chemical properties are compared to the desired properties of the layer to be formed. Based on this comparison, one or more other repeating units are selected, a test composition of such a polymer is made, formed into layers, and the physical and chemical properties are determined. As a non-limiting example of such a polymer design process, a homopolymer of several types of norbornene monomers is formed, then formed into a film, and contact angle and rolling angle are measured. Based on the homopolymer measurements described above, polymers with two or more types of repeat units can be used to achieve high contact angles and low tumbling angles and / or desired dissolution rates in basic aqueous solutions such as 0.26N TMAH. Can be formed.

Some embodiments according to the present invention are developable norbornene-based polymers useful for forming a photoresist composition. That is, unlike the embodiments useful for forming the topcoat layer discussed above, the polymer incorporated in the photoresist composition is a development type. Some such embodiments of the present invention include three or four different types of repeating units, while others include a greater or lesser number of types of repeating units. Will. Advantageously, several types of repeating units useful for developable polymers are those of formulas I-IV described above for non-self-developed polymers. Other useful types of repeat units for providing the developability of such developable polymers are of formulas V and VI described below:
[In Formula V: X and n are as defined for Formula I, and R ¹⁹ to R ²² are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹⁹ to R ²² is of the formula:
Wherein Q ^‡ is optional and, if present, is a linear or branched alkyl spacer of 1 to 5 carbons]
It is represented by In some other embodiments, the other R ¹⁹ to R ²² are each hydrogen and Q ^‡ is absent or is a linear alkyl spacer of 1 to 3 carbons. In other embodiments, the other R ¹⁹ to R ²² are each hydrogen and Q ^‡ is absent or 1 carbon atom, and in yet other embodiments, the other R ¹⁹ to R ²² are Each is hydrogen and Q ^‡ is absent. The repeating unit of formula V is generally for imparting hydrophilicity to the polymer. Unlike the topcoat or protective layer, as the hydrophilicity or wettability of the photoresist layer increases, the performance of the layer generally improves.

In Formula VI, X and n are as defined for Formula I, and R ²³ to R ²⁶ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ²³ to R ²⁶ is represented by the formula:
[Wherein Q ^‡ is as defined above and R ²⁷ is a linear or branched alkyl group of 1 to about 5 carbon atoms]
A group represented by one of H, J or K. It should be noted that the HJK (acid) group represented above is derived from one of the H, J or K groups. That is, some portion of the repeat unit represented by Formula VI and having at least one H, J, or K group therein is generally converted to HJK (acid) groups during polymerization separation after polymerization is complete. Converted. Thus, in embodiments according to the present invention comprising recurring units of the formula VI, generally a small fraction of these units have HJK (acid) groups, while the majority of such units are H, J Or one of the K groups. Such moieties shall be represented by formula VI (acid) to distinguish them from repeating units represented by formula VI. The repeating unit of formula VI provides a polymer with acid labile functional groups capable of forming acidic groups upon interaction with the PAG in the exposed areas of the photoresist layer, and the aqueous alkaline solubility of such exposed areas is To increase. When a repeating unit having such an acid labile group is present in the polymer chain, for example, chemical amplification as generally known is performed.

  Therefore, the embodiment of the developable polymer according to the present invention described above relates to a norbornene-based polymer useful for forming a photoresist composition and thus useful for forming a photoresist layer. In some such embodiments, the formed photoresist layer is suitable for direct contact with an immersion medium during an immersion lithography process. That is, such a development layer has a high contact angle, a receding angle, and a low sliding angle. In other embodiments, the development layer is best suited to underlie a protective layer during an immersion lithography process and exhibits little or no area mixed with such a protective layer forming composition. Advantageously, some embodiments of the present invention provide a developable polymer useful for forming a photoresist layer suitable for receiving a topcoat layer formed using the topcoat composition of the present invention. Embodiments.

  Embodiments according to the present invention comprise a developable polymer having more than one different type of repeating unit represented by one or more of the formulas I, II, III, IV, V, VI and / or VI (acid) When included, the molar ratio of such repeat units is such that repeat unit (1) is represented by formula I, repeat unit (2) is represented by formula V, repeat unit (3) is represented by formula VI, ( When the other of 4) to (m) is independently represented by the formula VI (acid), II, III or IV, the molar ratio of the polymer containing repeating units (1) :( 2) :( 3) : (4) :. . . : (M) is about (0-60): (5-60): (5-80): (0-15): (0-50):. . . : (0-50), where m is an integer representing a different last type of repeating unit and is generally 5 or less. In other such embodiments, the molar ratio is about (5-40) :( 10-50) :( 20-70) :( 1-10) :( 0-40):. . . : (0-40). Of course, it is understood that such a ratio cannot exceed 100 in total. In embodiments of the developable polymer of the present invention having repeating units of the type of formula I, V and VI, the type of formula I is generally 1-50 mol%, in some embodiments 10-40 mol%, The type of formula V should be in the range 1-50 mol%, in some embodiments 10-40 mol%, the type of formula VI in the range 20-75 mol%, and in some embodiments 30-50 mol%. Can do. When there is a repeat unit of the formula VI type, there is generally also a certain amount of a repeat unit of the formula VI (acid) type, and this amount of formula VI (acid) type generally reduces the amount of formula VI type. To do. Typically, the amount of formula VI (acid) type is less than 10 mol%. Of course, it should be understood that other polymer compositions having more or less of any particular type of repeating unit are also considered to fall within the scope and spirit of the invention. As discussed more fully below, the final preparation of the topcoat polymer is the result of certain design choices governed by the manner in which the topcoat layer formed from such a polymer is used.

(Monomer and polymerization)
Non-self-developing polymers as described above represented by one or more suitable repeating units of one or more types of formulas I, II, III, IV, V and / or VI, and developing polymers Are typically derived from suitable similar monomers. Thus, as a non-limiting example, a repeat unit, for example:
If desired, the following similar monomers:
Can be used to form the polymer.

  Thus, if a polymer having a first type of repeating unit of formula I and a second type of repeating unit of formula II, III, IV or V is desired, such a polymer is Similar monomers of the desired repeating unit can be prepared by appropriate addition polymerization (2, 3 chain); such addition polymerization can be carried out in the presence of a single or multi-component Group VIII transition metal catalyst. Will be implemented.

  If a multi-component catalyst is desired, it can be prepared in situ by combining a cocatalyst (or activator) and a procatalyst in the presence of the monomer (s) to be polymerized. Procatalyst means a Group VIII transition metal (generally palladium) containing compound that is converted to an active catalyst by reacting with a cocatalyst or activator compound. Descriptions and synthesis methods of representative procatalysts and cocatalysts, and cationic Pd (II) catalysts formed using them are known. For example, relevant portions are described in US Pat. No. 6,455,650, incorporated herein by reference. Where single component catalysts are desired, such catalysts (and some additional multi-component catalyst systems) are described in published US Pat. No. 20050187398, the relevant portions of which are hereby incorporated by reference. While such reference catalyst systems are briefly described below, it is understood that such descriptions provided herein are non-limiting examples and therefore are not all inclusive. Let's go. A more complete description of such catalyst systems is provided by the above-incorporated literature.

Suitable palladium procatalysts for the polymerization of the monomers of the present invention are the following formula A:
(Allyl) Pd (P (R ^x ) ₃ ) (L ′) (A)
[Wherein R ^x may be isopropyl or cyclohexyl; L ′ may be trifluoroacetate or trifluoromethanesulfonate (triflate)]
It is represented by Representative procatalysts of the invention having such a formula include, but are not limited to, (allyl) palladium- (tricyclohexylphosphine) triflate, (allyl) palladium (triisopropylphosphine) triflate, (Allyl) palladium (tricyclohexylphosphine) trifluoroacetate and (allyl) palladium (triisopropyl-phosphine) trifluoroacetate are included.

Other suitable procatalysts are described in the above-mentioned '650 patent and have the formula B:
[(E (R) ₃ ) _a Pd (Q) (LB) _b ] [WCA] _r (B)
[In the above formula, E (R) ₃ represents a group 15 neutral electron-donating ligand, E is selected from group 15 elements of the periodic table, and R is independently hydrogen (or its isotope). One) or an anionic hydrocarbyl (and its deuterium form) containing moiety; Q is an anionic ligand selected from carboxylate, thiocarboxylate, and dithiocarboxylate groups; Lewis base; WCA represents a weakly coordinating anion; a represents an integer of 1 or 2; b represents an integer of 1 or 2, where the sum of a + b is 3]
Including a palladium metal cation and a weakly coordinating anion.

Suitable single component catalysts are described in the above published applications and are represented by the following formulas B ′ and C:
[(E (R) ₃ ) _a Pd (Q) (LB) _b ] _p [WCA] _r (B ′)
[(E (R) ₃ ) (E (R) ₂ R ^* ) Pd (LB)] _p [WCA] _r (C)
It is represented by

In formula B ′, E, R, E (R) ₃ ; Q; LB and WCA are as defined for formula B, a represents an integer of 1, 2 or 3; b is 0; Represents an integer of 1 or 2, the sum of a + b is 1, 2 or 3; p and r represent multiples of palladium cations and weakly coordinated anions to balance the structural charge of formula B ′ Is an integer taken to In an exemplary embodiment, p and r are independently selected from an integer of 1 or 2.

In formula C, E (R ₃ ) is as defined for formula B ′; and E (R) ₂ R ^* represents a group 15 neutral electron donating ligand, where E, R , R and p are as defined above, R ^* is an anionic hydrocarbyl containing moiety, has a β hydrogen relative to the Pd center, and is bonded to Pd. In an exemplary embodiment, p and r are independently selected from integers of 1 and 2. Such single component catalyst systems can advantageously be used without the addition of a cocatalyst (i.e. as a latent catalyst activated only by the addition of energy, e.g. heating), but typically When such single component catalysts are used for solution polymerization, it is often desirable to add a predetermined amount of cocatalyst.

  Representative cocatalyst compounds include tetrakis (pentafluorophenyl) lithium borate / diethyl ether complex (LiFABA) and N-dimethylaniline / tetrakis- (pentafluorophenyl) borate (DANFABA), among others. Other suitable activator compounds are also described in the aforementioned '650 patent.

  In some multi-component catalyst embodiments of the present invention, the molar ratio of monomer to catalyst to cocatalyst is about 500: 1: 5 to about 20000: 1: 5 or 500: 1: 1 to 20000: 1: 1. Range. In some such embodiments, the molar ratio is from about 5000: 1: 4 to about 1000: 1: 2, and in still other embodiments, from about 3000: 1: 3 to about 1000: 1: 2. The molar ratio is advantageously. The appropriate molar ratio can and will vary depending on the activity of the particular catalyst system, the reactivity of the selected monomers, and the desired molecular weight of the resulting polymer. Also, in embodiments of the invention where a single component catalyst is used, the addition of a cocatalyst can be eliminated. However, in general, ratios of about 5000: 1: 4 to about 5000: 1: 2, especially about 2000: 1: 3 to about 1000: 1: 3 have been found useful.

  Suitable polymerization solvents for the addition polymerization reaction include aliphatic and aromatic solvents. These include aliphatic (nonpolar) hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2- Dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; esters such as ethyl acetate, i-amyl acetate; ethers such as diethyl Ethers; aromatic solvents such as benzene, toluene, o-, m- and p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, Freon® 112 halocarbon solvents, fluorobenzene, o-difluorobenzene , P-difluorobenzene, pentafluoro Benzene include hexafluorobenzene, and o- dichlorobenzene. Water may be used as a solvent. Other organic solvents such as diethyl ether, tetrahydrofuran, acetates (eg ethyl acetate), esters, lactones, ketones and amides may also be useful. Mixtures of two or more solvents are also useful.

  In a solution process, the polymerization reaction can be carried out by adding a preformed catalyst or a solution of individual catalyst components to a solution of norbornene-type monomer or monomer mixture to be polymerized. In some embodiments, the amount of monomer dissolved in the solvent is from about 5 to about 50% by weight (wt%), in other embodiments from about 10 to about 30% by weight, and in still other embodiments from about 10%. In the range of about 20% by weight. After the preformed catalyst or catalyst component is added to the monomer solution, the reaction medium is agitated (eg, stirred) to achieve thorough mixing of the catalyst and monomer component, and is generally heated for a time sufficient for polymerization.

  The reaction temperature of the polymerization reaction can range from about 0 ° C to about 150 ° C, but generally a temperature of about 10 ° C to about 100 ° C, or even about 20 ° C to about 80 ° C is advantageous. Has been found.

  In embodiments of the topcoat polymer of the present invention, the desired average molecular weight (Mw) of the polymer is from about 3000 to about 200000. In other embodiments, the Mw is from about 3500 to about 5000, and in yet other embodiments from about 4000 to 10,000. In embodiments of the photoresist polymer of the present invention, the desired Mw of the polymer is from about 2000 to about 50000. In other embodiments, the Mw is from about 2500 to about 35000, and in yet other embodiments, from about 3000 to 10,000. However, other embodiments of the present invention include topcoat and photoresist polymers having other ranges of average molecular weight, and such polymers may have Mw higher or lower than the exemplary Mw range described above. It must be understood. Thus, other Mw ranges are understood to fall within the scope and spirit of the present invention. In addition to the Mw range given above, the Mw of any polymer referred to herein should be measured using gel permeation chromatography (GPC) with an appropriate standard unless otherwise stated. Is noted.

(Polymer composition)
Some embodiments according to the present invention include compositions of the topcoat polymer embodiments or photoresist polymer embodiments discussed so far, such compositions having been previously disclosed. Appropriate polymers with any suitable repeating units can be introduced in molar ratios and Mw ranges. Such compositions are useful for forming films that are layered on a substrate as discussed in more detail below. Such a composition is a suitable polymer selected such that a film is formed on a substrate, for example a semiconductor substrate, and / or to achieve the desired performance of such a film in an immersion lithography process. A solvent, and one or more additional ingredients (additives).

  Initially referring to an embodiment of the invention that is a composition comprising a topcoat polymer, such a composition comprises a suitable amount of one or more different topcoat polymers, organic solvents, and optionally, as described above. Includes one or more acidic substances, a cross-linking material and a surfactant.

Useful organic solvents for the topcoat composition are those that can dissolve the polymer but are not miscible with the photoresist film already formed on the substrate. Such solvents generally include alcohol solvents having 1 to 10 carbon atoms, partially or fully fluorinated alcohol solvents having 1 to 10 carbon atoms, partial or having 4 to 15 carbon atoms, or Included are fully fluorinated alkyl ether solvents and partially or fully fluorinated alkyl ester solvents having 4 to 15 carbon atoms. Examples of solvents according to the above criteria are n-butyl alcohol, isobutyl alcohol, n-pentanol, 4-methyl-2-pentanol, 2-octanol, 2-perfluorobutylethanol (C ₄ F ₉ CH ₂ CH ₂ OH ), perfluoropropyl methanol _{((C 3 F 7) (} CH 2 OH)), H (CF 2) 2 CH 2 -O- (CF 2) 2 -H, H (CF 2) 7 - (CO) O- CH _3, and _{H (CF 2) 4 - (} CO) a _O-C 2 _{H 5.}

  In some cases, embodiments of the topcoat composition of the present invention can include an acidic compound. Advantageously, such acid compounds, when present, can act as a “post-exposure delay” protective agent. That is, if there is a delay in the timing between the imagewise exposure of the underlying photoresist film and the development of the formed image, such acid compounds can be present in any atmospheric amines or amine-containing materials that may be present. Can provide protection against impacts. Such protection interacts with the photoresist film exposed by the amines to prevent any such atmospheric amines before mispatterning of the photoresist film occurs during a delayed subsequent development process. This is accomplished by acidic compounds that react with the class to neutralize them. Therefore, by including an arbitrary acidic compound in the top coat composition, significant dimensional variation of the photoresist pattern due to the presence of amines or amine-containing compounds in the atmosphere can be reduced or eliminated.

Useful acidic compounds have the formula:
(C _p F _{2p + 1} SO ₂ ) ₂ NH X
[Wherein p is an integer of 1 to 5]
C _q F _{2q + 1} COOH XI
[Wherein q is an integer of 10 to 15]
[Wherein, r is an integer of 2 or 3, R ³¹ represents an alkyl group partially or wholly substituted with hydrogen or a fluorine atom, and the alkyl group further includes a hydroxyl group, an alkoxy group, a carboxyl group And may be substituted with any of amino groups]
[Wherein s is an integer of 2 or 3 and R ³¹ is as defined above]
It is represented by

Examples of acidic compounds are (C ₄ F ₉ SO ₂ ) ₂ NH, (C ₃ F ₇ SO ₂ ) ₂ NH, C ₁₀ F ₂₁ COOH,
It is.

  In some topcoat composition embodiments of the invention, an optional crosslinker is added. Such optional cross-linking agents are generally nitrogen-containing compounds having an amino group and / or an imino group, wherein at least two hydrogen atoms are substituted with a hydroxyalkyl group and / or an alkoxyalkyl group. Such crosslinking agents include, but are not limited to, melamine derivatives, urea derivatives, guanamine derivatives, acetoguanamine derivatives, benzoguanamine derivatives, and succinylamide derivatives, in which the hydrogen atom of the amino group is a methylol group or an alkoxymethyl group. Or those substituted with both of them; and glycoluril derivatives and ethylene-urea derivatives in which the hydrogen atom of the imino group is substituted. An example of a cross-linking agent is tetrabutoxymethylated glycoluril.

  These nitrogen-containing compounds are prepared by reacting, for example, melamine derivatives, urea derivatives, guanamine derivatives, acetoguanamine derivatives, benzo-guanamine derivatives, succinylamide derivatives, glycoluril derivatives, or ethylene-urea derivatives in formalin and boiling water. It can be obtained by methylation or further alkoxylation by reacting it with a lower alcohol, specifically methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol. One example of a cross-linking agent that has been found to be useful is tetrabutoxymethylated glycoluril.

  Other crosslinkers have also been found useful. For example, a condensation product of a monohydroxy-monocarboxylic acid compound with at least one type of hydrocarbon compound substituted with a hydroxyl group and / or an alkoxy group is also included. Exemplary condensation products include monohydroxy-monocarboxylic acids in which the hydroxyl and carboxyl groups are bonded to a single carbon atom or adjacent carbon atoms.

  If desired, the protective film-forming composition according to embodiments of the present invention can further comprise any surfactant added thereto. An example of the surfactant is XR-104 (trade name of Dainippon Ink and Chemicals, Inc.), but the present invention is not limited to this. By adding a surfactant to the material, it becomes possible to improve the coverage of the material and the ability to provide a more uniform coatability of the topcoat or protective film. This increase in uniformity is a result of suppressing unevenness of the film.

  Embodiments of the topcoat composition of the present invention are used to form a topcoat or protective layer film that overlays a photoresist film formed on a substrate. Such films are generally for receiving immersion fluids such as those used in immersion lithography processes. Generally, the thickness of such a topcoat film is from about 70 nm to about 200 nm in some embodiments, but in other embodiments from about 90 nm to about 180 nm, and in still other embodiments, about 120 nm. ~ About 160 nm. However, it will be appreciated that other film thicknesses above or below the above ranges are also useful and thus fall within the scope and spirit of embodiments of the invention. Furthermore, the thickness of any particular film obtained by appropriate use of the topcoat composition of the present invention is dependent on the coating method used and the amount of topcoat polymer present in such composition, and optionally It will be understood that this depends on the amount of additive. When a spin coating method is used (described in further detail below), in some embodiments, the desired range of topcoat polymer amount is from about 0.1 wt% (wt%) to about 30 wt%. And in other embodiments, such amounts are from about 0.3% to about 15% by weight, and in yet other embodiments from about 0.5% to about 7.5% by weight. Is desirable. Such weight% values are relative to the total amount (weight) of the topcoat composition. However, it is understood that ranges of the amount of topcoat polymer that are above or below the above range are also useful and thus fall within the scope and spirit of embodiments of the present invention.

  When optional surfactants are added to such topcoat compositions, in some embodiments from about 0.001% to about 10%, in other embodiments from about 0.01% to about 1% by weight, and in yet other embodiments in the range of about 0.05% to about 0.5% by weight of such surfactants are used, such amounts being the topcoat polymer in the composition It is for the amount of. When optional cross-linking agents are added to such topcoat compositions, in some embodiments from about 0.5% to about 10%, in other embodiments from about 1% to about 8%, In still other embodiments, such surfactants in the range of about 3% to about 7% by weight are used, and such amounts are relative to the amount of topcoat polymer in the composition. When any acidic compound is added to such a topcoat composition, in some embodiments from about 0.1 wt% to about 10 wt%, in other embodiments from about 0.2 wt% to about 5 wt%. Such acidic compounds are used in weight percent, and in yet other embodiments in the range of from about 0.3 weight percent to about 1 weight percent, and such amounts are relative to the amount of topcoat polymer in the composition. It is.

  Reference is now made to embodiments of the invention which are compositions comprising a developable or photoresist polymer, such compositions comprising an appropriate amount of one or more of the photoresists or developable polymers discussed above. An organic solvent, a photoacid generator material, optionally an amine material, and a group of one or more miscible additives (described in detail below). Further, some embodiments are photoresist compositions that act positively (“positive tone” or “positive type”). That is, after imagewise exposure of a layer of such composition formed on a substrate, the pattern formed is the result of removal of the exposed area of the layer or has been "developed-out". As a result, only the non-exposed areas of the layer remain on the substrate.

  Preferred solvents for embodiments of the photoresist composition of the present invention are selected for their ability to provide a polymer suitable for coating a film of such composition on a substrate as well as a solution of any of the additives described above. The Those skilled in the art are aware that any of the exemplary solvents listed below, whether alone or in any combination thereof, or used in conventional chemically amplified resists not listed below. The solvent or solvents that fall within the scope or spirit of embodiments of the photoresist composition of the present invention.

  Examples of solvents are generally organic solvents such as ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate. , Propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate; cyclic ethers such as dioxane; and esters such as Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate , Methyl methoxypropionate, and ethyl ethoxypropionate. As mentioned above, exemplary solvents can be used alone or as a mixture of two or more different individual solvents. When mixed solvents are used, it has been found that a mixed solvent of propylene glycol monomethyl ether acetate and lactic acid ester is generally advantageous, especially when used in a mixing ratio of about 8: 2 to 2: 8 (mass), respectively. The

  In some photoresist composition embodiments, a mixed solvent comprising at least one of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) with γ-butyrolactone (GBL) as the organic solvent is advantageous. It has been found to be. In such a case, the weight ratio of the former and latter components of such a mixed solvent is about 70:30 to about 95: 5. A weight ratio of 50:50 to about 90:10 is useful when both PGMEA and EL are used.

In order to realize this developability of such a positive resist composition, a photoacid generator (PAG) component is provided. Such components produce acid when exposed to a suitable energy source such as ultraviolet light having a peak wavelength at 193 nm (ArF excimer laser) or 157 nm (F ₂ excimer laser). The resulting acid then deprotects some protected pendant groups of the resin's repeat units, resulting in an increase in the dissolution rate in the exposed area relative to the dissolution rate in the unexposed area. Useful PAG components can be appropriately selected from any known materials conventionally used as photoacid generators in chemically amplified resists. Examples of PAGs include, but are not limited to, onium salts such as (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenyl Sulfonium trifluoromethanesulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, bis (p- tert-butylphenyl) iodonium nonafluorobutanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, and diphenyliodonium trifluoromethanephosphate.

  It is understood that the photoacid generator component of the photoresist composition according to the present invention can utilize a single PAG or a combination of two or more PAGs. Further, the appropriate amount of such PAG (s) introduced into certain photoresist compositions is typically about 0.5 to about 30% by weight, but with other such compositions About 1 to about 10% by weight. In general, if the amount of PAG component is less than about 0.5% by weight, there will be problems with imaging in the exposed layer, while if it exceeds about 30% by weight, it will be difficult to achieve a homogeneous solution. In such a case, the storage stability of such a composition may be deteriorated.

  Any amine additive may be used in some photoresist embodiments of the present invention. Such amine additives sometimes improve the shape of the resist pattern and the long-term stability in the photoresist layer (post-exposure stability of the latent image formed by imagewise exposure of the resist layer). Has been found. Generally, a lower aliphatic secondary or tertiary amine is added. Lower aliphatic amine means an alkylamine or alkylalcoholamine having 5 or less carbon atoms. Exemplary amines include, but are not limited to, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine and triethanolamine. In many cases, trialkanolamines have been found to be advantageous. As can be seen with respect to solvents and PAGs, the optional amine component may be a single amine or any suitable combination of two or more amines. In general, when used, such optional amine additives are present in the range of about 0.01 to 5% by weight in some embodiments, but from about 0.01 to about 2% by weight in other embodiments. And such amounts are relative to the amount of polymer.

  In some embodiments of the invention, other optional additives are used. All such optional additives are miscible and are selected as needed and included in the composition. That is, certain properties of the composition or the resulting layer are improved. Exemplary optional miscible additives include, but are not limited to, surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants and antihalation agents to improve ease of application. included.

(Immersion lithography process)
In some immersion lithography process embodiments according to the present invention, the development polymer composition embodiment described above (photoresist composition) is used to form a development layer that is overlaid on a substrate such as a semiconductor substrate. Is used. In such an embodiment, first, using a spinner, a photoresist composition is applied to a substrate surface, such as a silicon wafer, to form a photoresist layer having a first desired thickness. The layer is then pre-fired and imagewise exposed using, for example, an ArF excimer laser (193 nm) through the desired mask pattern. After exposure, the layer is post-exposure baked (PEB) and then cooled and developed using an alkaline developer. Generally, the precalcination is from about 70 ° C. to about 140 ° C. for about 40 to about 120 seconds, and in some embodiments, about 60 to about 90 seconds (sec). PEB is generally performed at the same time and temperature as the precalcination process. The alkaline developer is generally a 0.1-10 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), typically a 0.26N TMAH solution. In this way, a resist pattern faithful to the mask pattern can be obtained.

In addition, although ArF excimer lasers have been found to be advantageous for developing photoresist layers formed from the developable polymer compositions of the present invention, other types of radiation can also be used for patterned photons. It should be noted that it is effective for forming a resist layer. For example, at longer wavelengths such as 365 nm and shorter wavelengths obtained with F ₂ lasers etc., EUV (extreme ultraviolet) sources, VUV (vacuum ultraviolet) sources, electron beams, X-rays and soft X-rays are also effective. Can be used.

  In some development process embodiments of the present invention, the previously described topcoat polymer composition embodiments may be combined with a protective layer on the already formed photoresist layer before the photoresist layer is imagewise exposed. Used to form. Generally in such an embodiment, a photoresist layer is formed on the substrate, and after pre-baking such a layer, a topcoat composition is applied onto the photoresist layer using a spinner, and the A top coat layer is formed thereon, and such a top coat layer has a second desired thickness. After the topcoat layer is applied, preliminary baking is performed on the photoresist layer in the same manner as described above. After pre-baking the topcoat layer, the underlying photoresist layer is imagewise exposed as described above, followed by PEB and development. Advantageously, the topcoat layer of the present invention is soluble in the aqueous alkaline developer solution used. Thus, when exposed to such a solution, the topcoat layer is immediately removed and the photoresist layer is completely presented to the developer. In this way, a resist pattern faithful to the mask pattern can be obtained without requiring a separate top coat removing step. It should be noted that the topcoat layer forming composition of the present invention is suitable for use with any suitable photoresist material, where appropriate refers to the protective layer forming composition and most Or the substance which does not show mixing property at all.

  The following description of a lithographic system that can be used with the topcoat composition and / or photoresist composition described above in forming each includes a plurality of integrated circuits (ICs) formed on / in a semiconductor substrate (wafer). Is provided in the exemplary sense of manufacturing. Examples of ICs include general purpose microprocessors made from thousands or millions of transistors, dynamic, static or flash memory arrays, or any other dedicated circuitry. However, those skilled in the art can apply the methods and apparatus described herein to the manufacture of any product manufactured using lithography, such as micromachines, disk drive heads, DNA chips, micromachine technology (MEMS), etc. You will see that.

  Exemplary IC processing apparatus can include an immersion lithographic apparatus used to image a pattern on a wafer or wafer area. A photoresist composition or development layer is overlaid on the wafer. For example, the lithographic apparatus may be a step-and-repeat exposure apparatus or a step-and-scan exposure apparatus, but is not limited to these exemplary apparatuses. The lithographic apparatus can include a structure (often referred to as a reticle) that directs light energy in the direction of the light source and lens array or mask, and then to the development layer on the substrate. The light energy typically has a wavelength of 193 nm, although other wavelengths such as 157 nm or 248 nm can also be used.

  The mask selectively blocks light energy so that the light energy pattern defined by the mask is transferred to the wafer. A development subsystem, such as a stepper or scanner device, continuously directs the energy pattern conveyed by the mask to a series of desired locations on the wafer. The development subsystem may include a series of lenses and / or reflectors used to scale the energy pattern and direct it to the wafer in the form of a development (or exposure) light energy pattern.

  The development pattern (or exposure pattern) is generally conveyed by the development subsystem through an immersion medium having a relatively high refractive index (eg, a refractive index greater than 1 but less than the refractive index of the development layer). The immersion medium is generally a liquid. In one example, purified deionized water is used with a 193 nm light source (eg, an argon fluorine (ArF) laser).

  Embodiments of the topcoat composition according to the present invention can be used to form a topcoat layer that covers the photoresist development layer. Such a topcoat layer accepts an immersion material and prevents or inhibits such immersion media and components thereof from entering the underlying development layer. In this way, adverse effects in development can be prevented or at least inhibited. Such an adverse effect is an effect caused by the above-described problem.

  Embodiments of the photoresist composition according to the present invention can be used to form a photoresist layer covering a substrate. Such a photoresist layer is advantageously able to accept the immersion medium directly since its hydrophobicity is considered high enough to prevent or inhibit the penetration of the immersion medium or its components. In this way, adverse effects in development can be prevented or at least inhibited. Such an adverse effect is an effect caused by the above-described problem. In some method embodiments according to the present invention, the photoresist composition embodiment of the present invention is used to form a photoresist layer over a substrate, and the topcoat composition embodiment is already formed. Used to form a topcoat layer overlying the exposed photoresist development layer.

  Thus, in some embodiments of the present invention, the process for producing an image on a substrate is: (a) First, a photoresist composition is coated on the substrate to form a developer layer thereon. (B) secondly, a topcoat composition according to the present invention is coated on a substrate to form a topcoat layer covering the development layer; (c) the substrate and the coating layer are imaged with appropriate irradiation rays; (D) developing. In another embodiment, the first coating described above uses a photoresist composition according to the present invention and does not include a second coating, but in yet another embodiment, the first coating and the second coating. Both coatings use a suitable composition of the present invention. Further, in step (a) above, the photoresist composition essentially interacts with the solvent or topcoat polymer used to form the castable composition once formed into a layer. It should be noted that any composition that does not.

  In each of the processes described above, the first coating includes coating the substrate with a film that includes a photoresist composition. Suitable substrates include silicon, ceramic, polymer and the like. Suitable photoresist compositions can be those according to the present invention, ie, compositions comprising embodiments of the polymeric material of the present invention, as well as other photoresist compositions. The second coating, if implemented, overlays the film formed from the topcoat composition according to the present invention on the development layer. Such a topcoat layer or film is typically formed in a manner similar to the formation of the photoresist layer. Imagewise exposure includes exposing a selected portion of the development or photoresist layer to appropriate radiation. Finally, development involves developing the image created by imagewise exposure by first removing any topcoat layer that may have been formed. Because any topcoat layer formed using the topcoat composition according to the present invention is soluble in a base type aqueous solvent as also used to develop images in typical development layers. In embodiments of the present invention, the same solvent can be utilized for both topcoat removal and development. In some embodiments, a single process can be used for both topcoat removal and development. Suitable solvents include aqueous bases, such as aqueous bases free of metal ions, such as tetramethylammonium hydroxide or choline.

  The invention also relates to an integrated circuit assembly, for example an integrated circuit chip, multichip module or circuit board, manufactured by the method of the invention. The integrated circuit assembly includes circuitry formed on the substrate by any of the coating, exposure and development methods described above.

  After exposing, developing and etching the substrate, the substrate is coated with a conductive material such as a conductive metal by techniques known in the art, such as vapor deposition, sputtering, plating, chemical vapor deposition, or laser induced vapor deposition. A circuit pattern can be formed in the exposure region. The surface of the film can be polished to remove any excess conductive material. It is also possible to deposit a dielectric material by a similar technique during the circuit manufacturing process. In the process of manufacturing a p- or n-type doped circuit transistor, inorganic ions such as boron, phosphorus or arsenic can be implanted into the substrate. Other techniques for forming circuits are well known to those skilled in the art.

  The photoresist layer and / or topcoat layer using the composition according to the invention can be formed by known spin coating techniques or any other suitable coating method. The topcoat composition can be applied on any photoresist development layer to form a layer over it by such coating methods. The thickness of the topcoat or development layer formed using a suitable composition that is an embodiment of the present invention generally ranges from about 10 nanometers (nm) to about 300 nm. In some embodiments, it can be about 20 nm to about 200 nm, and in other embodiments about 30 nm to 160 nm. It should be noted that other thicknesses of both the topcoat and development layers, greater or smaller than any of the above ranges, have also been found useful, and thus fall within the scope and spirit of the present invention. is there.

  Typically, once formed, the topcoat layer exhibits one or more of the following desired properties: 1) to an aqueous base developer (eg, 0.26N tetramethylammonium hydroxide (TMAH)). Fast dissolution; 2) high transparency at the wavelength used for imagewise exposure, eg 193 nm, and / or 3) a suitable refractive index, eg a refractive index of about 1.5 at 193 nm. The first property is desired so that the topcoat layer is immediately incorporated into a typical patterning process flow. The second property is desired so that the topcoat layer does not interfere with the lithographic operation of the development layer. A third property may be desired if necessary when the topcoat layer can act as an antireflective layer when water is used as the immersion layer.

  When a development layer is formed from an embodiment of the composition of the present invention, such a layer typically exhibits the following properties: a) when a topcoat layer is used, than the topcoat layer Limited dissolution of the unexposed areas of the layer in an aqueous base developer (eg, 0.26N tetramethylammonium hydroxide (TMAH)) at a slow rate; 2) a topcoat coated using the topcoat composition When forming a layer, there should be little or no interaction with the solvent used to form the topcoat composition; 3) high sensitivity to wavelengths used for imagewise exposure; 3) line edge roughness Resolution of shapes with dimensions of about 65 nm or less with little or no; and 4) Excellent resistance to subsequent processes such as reactive ion etching processes.

  The following examples include detailed descriptions of the polymerization and the monomers used therein. Such a description can be used to produce the polymers used in embodiments of the present invention. While these examples and the materials described therein fall within the scope and spirit of the embodiments of the present invention, they are provided for purposes of illustration only and are intended to limit the scope and spirit of the invention. It is not a thing. Other examples provided herein relate to the properties of polymers and polymer compositions that are embodiments of the present invention. Such properties are of interest to enable embodiments of the polymer design of the present invention and to demonstrate that the polymers and polymer compositions of the present invention are useful in the immersion lithography process described herein.

As used in the polymerization examples and specifications, the ratio of monomer to catalyst and cocatalyst is a molar ratio. Further, although the term “sparged” or “sparged” will be used repeatedly in the examples, such terms will be understood to mean passing nitrogen gas through the liquid to remove dissolved oxygen. . Still further, in the examples, many acronyms or abbreviations are used. To assist in understanding these examples, a list of such acronyms or abbreviations is then provided below along with their full meanings:
Acid NB: Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid THF: Tetrahydrofuran MeOH: Methanol PGMEA: Propylene glycol methyl ether acetate Mw: Weight average molecular weight Mn: Number average molecular weight PDI: Polydispersity ( (PDI = Mw / Mn)
¹ H-NMR: proton nuclear magnetic resonance spectroscopy
¹⁹ F NMR: fluorine nuclear magnetic resonance spectroscopy
¹³ C NMR: carbon nuclear magnetic resonance spectroscopy Pd1206: bis (triisopropylphosphine) palladium acetate-acetonitrile complex tetrakis (pentafluorophenyl) borate Pd1394: (acetonitrile) bis (t-butyldicyclohexylphosphine) palladium acetate-acetonitrile Complex ・ Tetrakis (perfluorophenyl) borate LiFABA ： Tetrakis (pentafluorophenyl) lithium borate ・ Diethyl ether complex DANFABA ： N-Dimethylaniline ・ Tetrakis- (pentafluorophenyl) borate

The following monomer and monomer precursor structures shown in structural groups AA, BB and CC with appropriate acronyms or abbreviations are also provided to further assist in understanding the examples. In addition, the monomers designated PPVENB in Group BB were obtained from DuPont FluoroIntermediates of Wilmington, Delaware, and the monomers designated C10FAcNB, C8AcNB, C8GAcNB, C9BrAcNB, C10BrAcNB and FHCNB are Texas Rounds. Note that it was obtained from Exfluor Research Corporation of Rock.

  The measurement of CA, SA and dissolution rate was performed by one of two procedures. For each measurement of each type, the film of interest is formed on the substrate and the measurement reported is for that film. If applicable, measurement method 1 was used in Examples P4-P29, and measurement method 2 was used in the other examples.

  Measurement method 1: (a) Contact angle: 3 μL of pure water droplets were placed at three different positions on the wafer, and the contact angle of the water droplets at each position was measured using a commercially available contact angle goniometer (Rame-Hart model # 100-00). Reported values are the average of three measurements; (b) Fall angle: 50 μL on coated substrate positioned on proprietary equipment capable of increasing substrate tilt angle from horizontal position (tilt angle = 0) Distributed. The inclination angle at which the water droplet started to slip was defined as the falling angle. Reported values are the average of two measurements; (c) Dissolution rate: The film of interest was formed from a 20% solution of the polymer of interest dissolved in isobutanol. The forming process was adjusted to obtain a formed film of about 300 nm ± 75 nm. The initial film thickness and Cauchy parameters A and B were measured by ellipsometry. The sample was then dipped in 0.26N tetramethylammonium hydroxide (TMAH) for 3 seconds, drawn, rinsed with deionized water, and dried using a stream of dry nitrogen. After drying, the film thickness was measured again and the dissolution rate was reported as the change in thickness divided by the immersion time. Upon remeasurement, a dissolution rate of> 100 nm / sec was reported if the film was completely removed on the substrate.

  Measurement method 2: (a) Contact angle: A film having a thickness of about 140 nm was formed. Using “Drop Master 700” (Kyowa Interface Science Co., Ltd.) in an environment with a temperature of about 25 ° C. and a relative humidity of 50%, 2 μL of pure water was dropped on the film; . The rolling angle or sliding angle was measured as follows: A protective film forming material was applied to a silicon wafer to form a protective film having a thickness of 140 nm. Using “Drop Master 700” (Kyowa Interface Science Co., Ltd.) in an environment with a temperature of about 25 ° C. and a humidity of about 50%, 50 μl of pure water was dropped onto the substrate at an inclination rate of 1 ° / second. (C) The dissolution rate (solubility) in the developer was measured as follows: a protective film-forming substance was applied to a silicon wafer to form a protective film having a thickness of 350 nm. Using “RDA-800” (Litho Tech Japan Co., Ltd.), the substrate was brought into contact with a 2.38 wt% TMAH aqueous solution (23.5 ° C.) for 120 seconds. The water resistance was measured as follows: A protective film forming material was applied on a silicon wafer to form a protective film having a thickness of 140 nm. Using “D-SPIN8” (Dainippon Screen MFG Co., Ltd.), the substrate was brought into contact with pure water (23.5 ° C.) for 120 seconds.

  Measurement of optical density (OD). Samples were prepared by spin coating a 1 inch quartz wafer with an approximately 15 wt% solution of the desired polymer, typically in propylene glycol methyl ether acetate (PGMEA). Samples were baked on a hot plate at 130 ° C. for 60 seconds and then allowed to cool and their respective optical absorption was measured at 193 nm using a Cary 400 Scan UV-Vis spectrophotometer. A blank quartz wafer was used for the reference beam. In order to measure the film thickness of each sample, a part of the film was removed from the quartz wafer, and the thickness was measured using a Tencor surface shape measuring device. The optical density was calculated as absorbance / thickness (in microns). It should be noted that all OD measurements gave values sufficiently low to allow exposure of the underlying photoresist layer without visible image degradation.

Example of monomer synthesis Example MS1 secPrHFAEsNB
Dicyclopentadiene (60 g, 0.45 mol) was placed in a 200 mL round bottom flask equipped with a short path distillation head. The flask was heated and a cyclopentadiene distillate was collected at 30-32 ° C. In a separate 500 mL three-necked round bottom flask maintained in a nitrogen atmosphere was added acrylic acid 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-1-butyl ester (50 g, 0.18 mol). ) And toluene (125 mL). Separately, cyclopentadiene (22-23 mL, 0.28 mol) obtained by distillation was added by syringe through a rubber septum. After this addition, the flask and its contents are heated to about 35 ° C. and the temperature is allowed to reach that temperature for about 19 hours until gas chromatography (GC) analysis of the reaction mixture shows complete conversion of the starting material. Maintained. Concentration of the product in toluene using a rotary evaporator and distillation under reduced pressure using a short path distillation head yielded a secPrHFAEsNB monomer product between about 65-70 ° C./170 mmHg. The yield of 99% pure monomer determined by GC was about 95%. The structure was confirmed using ¹ H-NMR analysis.

Example MS2 TFSCH ₂ NB
Norbornene ethylamine (NBCH ₂ CH ₂ NH ₂ ) is first reacted with nitromethane and 5-norbornene-2-carboxaldehyde (NBC (O) H) in the presence of sodium hydroxide in methanol, followed by aluminum hydride. Obtained by selective reduction of the nitroethyl pendant group with lithium. This synthetic method is reported by Kas'yan et al., Russ. J. Org. Chem. 2002, 38 (1), 29-35. Norbornene ethylamine was reacted with trifluoromethanesulfonic anhydride in the presence of triethylamine to produce the target monomer TFSCH ₂ NB.

Examples MS3 NBXOCH ₃ and MS4 NBCH ₂ OC ₃ H ₇
A 60% dispersion of sodium hydride in the amount shown in Table A was mixed with anhydrous THF (150 mL) and cooled in an ice bath. Under a nitrogen atmosphere, X shown in Table A was added slowly (30 minutes) to the stirred suspension.

  The mixture was refluxed for Y hours at 60-65 ° C., Z was added and heating was continued for the times shown in Table A. The reaction mixture was filtered. The solvents shown in Table A were added to the filtrate and washed with water, 10% sulfuric acid and water again as shown in Table A. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The crude product was distilled under reduced pressure to give the% target compounds shown in Table A.

Example MS5 NBHFAEsNB
Trifluoroacetic acid (117 g, 1.02 mol) was added to a solution of HFANB (140 g, 0.511 mol) in toluene (240 mL). The mixture was then stirred for 20 hours at room temperature under a nitrogen atmosphere, after which it was diluted with excess toluene and the toluene solution was washed with water (250 mL) and brine (300 mL). The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The crude product was purified by vacuum filtration, yielding 175 g of intermediate HFANBOCOCF ₃ .

HFANBOCOCF ₃ obtained above (175 g, 0.450 mol) was mixed with water (750 mL), methanol (300 mL) and sodium hydroxide (30 g, 0.75 mol) and then stirred at room temperature for 1.5 hours. . Hydrochloric acid solution (10%) was added to make a solution with a pH of 1-2 and separation into two layers was observed. The first organic layer (lower layer) is removed, the upper aqueous layer is washed with toluene (2 × 300 mL), the resulting toluene layer is mixed with the first organic layer, these mixed layers are then washed with water ( (300 mL) and 10% sodium chloride (300 mL), separated and dried over anhydrous magnesium sulfate. When toluene was removed, 140 g of crude HFNBOH was obtained.

HFNBOH (50 g, 0.17 mol) obtained above was dissolved in 300 mL anhydrous THF and cooled in an ice bath. Under a nitrogen atmosphere, a syringe was used and n-butyllithium (160 mL of a 2.5 M solution in hexane, 0.4 mol) was added through a rubber septum. The solution was allowed to come to room temperature while stirring for 5 hours. The solution was then cooled to 0-5 ° C. with stirring and acrylyl chloride (18.1 g, 0.2 mol) dissolved in 50 mL anhydrous THF was added with continued stirring. After the acrylyl chloride addition was complete, the solution was allowed to come to room temperature and kept stirring overnight. The reaction mixture was then acidified to pH˜4 using 5% hydrochloric acid solution. Two layers were formed and the organic layer was separated and concentrated using a rotary evaporator and then dissolved in diethyl ether (300 mL). The ether solution was washed with water (2 × 200 mL) and brine (2 × 200 mL), dried over anhydrous magnesium sulfate and concentrated. The product (HFANBOCOCHCH ₂ ) was purified by distillation under reduced pressure.

HFANBOCOCHCH ₂ (28.0 g, 0.081 mol) obtained above was dissolved in 100 g of toluene. Cyclopentadiene (16.0 g, 0.24 mol) was added to the solution and stirred at room temperature for 16 hours under a nitrogen atmosphere. Toluene was removed on a rotary evaporator at 50-60 ° C and the crude product was heated to 40-60 ° C under vacuum for 1.5-2 hours. The final product, NBHFAEsNB, was purified by column chromatography using silica gel.

  The next two examples are fully or partially anticipated examples for monomer synthesis. That is, although some or all of the specific procedures provided below have not yet been performed, we believe that the proposed results will be achieved by well-known chemical processes. Yes.

Expected Examples of Monomer Synthesis Example MS1p TFSnPrNB
NBCH ₂ CH ₂ CH ₂ Br is obtained by Diels-Alder reaction and converted to NBCH ₂ CH ₂ CH ₂ CN using known chemical reactions. Next, the obtained nitrile is chemically reduced using lithium aluminum hydride to produce an amide, and then treated with trifluoromethanesulfonic anhydride to obtain the target compound.

Example MS2p TFSsecPrNB
Part of this synthesis is a modification of the original literature report: Kas'yan et al., In Russian Journal of Organic Chemistry 2002, 38 (1), 29-35. Sodium hydroxide (29.5 g, 0.738 mol) was dissolved in deionized water (75 g) and cooled in an ice bath. Norbornene carboxaldehyde (50.0 g, 0.410 mol), nitroethane (32.3 g, 0.431 mol) and methanol (300 mL) were placed in a 1 L three-necked round bottom flask and about −5 in an ice-cold water / salt bath. It cooled from -10 degreeC to -10 degreeC. While maintaining the temperature at −5 ° C. or lower, a cold aqueous sodium hydroxide solution was added dropwise to the flask. The solution was brought to room temperature in 2 hours and continued to stir at room temperature for 15 hours. The resulting white solid was partially dissolved in ice cold water (500 mL). This suspension was added to a 20% hydrochloric acid solution (600 mL) and extracted with methylene chloride (2 × 300 mL). The methylene chloride extract was washed with brine (2 × 250 mL), dried over anhydrous magnesium sulfate, filtered and concentrated. The crude product was distilled under reduced pressure to obtain the target compound (NBCH = C (CH ₃ ) NO ₂ ) in a yield of 47%.

The nitro compound (NBCH = C (CH ₃ ) NO ₂ ) is thought to be selectively reduced by lithium aluminum hydride to yield the corresponding amine NBCH ₂ CH (CH ₃ ) NH ₂ . Furthermore, it is thought that it is induced | guided | derived to a sulfonamide product (TFSsecPrNB) by making it react with a trifluoromethanesulfonic acid chloride or a trifluoromethanesulfonic acid anhydride in presence of a triethylamine base.

Example P1; P2 and P3
TFSNB and HFANB, FPCNB or C8AcNB polymers The variables for these examples are shown in Table B. To a glass reaction vessel equipped with a stirrer, TFSNB toluene; ethyl acetate; and one of HFANB, FPCNB, or C8AcNB was added. The mixture was sparged and placed in a drying box where solid DANFABA and triethylsilane were added. The reaction vessel was removed from the drying box and sparged glacial acetic acid was added. The mixture was then heated to 100 ° C. and Pd-1206 in ethyl acetate was added. The mixture was maintained at 100 ° C. with stirring for the indicated time and then allowed to cool to room temperature. Total solids showed essentially 100% conversion of the monomer. Each reaction mixture was purified to remove residual monomer and catalyst. The analytical data obtained are shown in the following table.

Examples P4 and P5
Homopolymers of secPrHFAEsNB and TFSCH ₂ NB The variables for these Examples P4 and P5 are shown in Table C. In Example P4, secPrHFAEsNB monomer and anhydrous toluene (30 mL) were mixed in a 100 mL crimp cap vial and purged with nitrogen for 10 minutes and sealed. The vial was moved to the dry box, the seal was broken, Pd-1394, LiFABA and triethylsilane were added and the vial resealed. Glacial acetic acid was then added by syringe. The reaction mixture was heated in an oil bath at 90 ° C. for about 23 hours, resulting in a clear yellow liquid. After purification to remove residual monomer and catalyst, the reaction mixture was precipitated using hexanes and dried at 90 ° C. under reduced pressure.

In Example P5, TFSCH ₂ NB, toluene, and ethyl acetate were added to a glass reaction vessel equipped with a stirrer. The mixture was sparged, then placed in a dry box and solid DANFABA, Pd-1206 and triethylsilane were added. The reaction vessel was removed from the dry box and sparged glacial acetic acid was added. The mixture was heated at 100 ° C. for 17.5 hours and then allowed to cool to room temperature before being purified to remove residual monomer and catalyst. The analytical data obtained are shown in the following table.

Example P6; P7 and P8
The variables of Examples P6, P7 and P8 are shown in Table D. In P6 and P7, TFSNB, HFANB, toluene and ethyl acetate were added to a glass reaction vessel equipped with a stirrer, sparged, and moved to a dry box. In Example P8, TFSNB, HFANB, toluene and ethyl acetate were added in a dry box. Solid DANFABA, Pd-1206 and triethylsilane were added to the reaction vessel, the reaction vessel was sealed and removed from the dry box. Sparged glacial acetic acid was added to the reaction mixture and then brought to 100 ° C. with stirring for the time indicated in Table D. The reaction mixture was left to cool to room temperature. Quantification of the total solids content of the reaction mixture showed that essentially 100% conversion of the monomer occurred. The reaction mixture was purified to remove residual monomer and catalyst. In P8, the purification involved the precipitation of the polymer from hexane, the precipitate was collected by filtration and dried in vacuo at 90 ° C. The obtained analytical data is shown in the table.

Example P9; P10 and P11
Polymers of TFSNB and BuNB, C8AcNB and secPrHFAEsNB The variables of Examples P9, P10 and P11 are shown in Table E. In P10 and P11, TFSNB, toluene, ethyl acetate, and one of C8AcNB or secPrHFAEsNB were added to a glass reaction vessel equipped with a stirrer, the mixture was sparged, and then the reaction vessel was placed in a dry box. In P9, the reaction vessel was placed in a dry box before adding TFSNB, BuNB, toluene and ethyl acetate. While stirring, triethylsilane; Pd-1206; and DANFABA were added to the dry box, and the reaction vessel was capped and removed from the dry box. Sparged glacial acetic acid was added and the mixture was heated to 100 ° C. for the length of time indicated in the table, then allowed to cool to room temperature. The reaction mixture was added into hexane to precipitate, and the polymer was collected by drying at 90 ° C. under reduced pressure. The obtained analytical data is shown in the table.

Example P12; P13 and P14
Polymers of TFSNB and secPrHFAEsNB, C9BrAcNB or C10BrAcNB The variables of Examples P12, P13 and P14 are shown in Table F. In P13 and P14, a glass reaction vessel equipped with a stirrer was placed in a dry box, and TFSNB, toluene, ethyl acetate, and one of C9BrAcNB or C10BrAcNB were added. At P12, TFSNB, secPrHFAEsNB, toluene, and ethyl acetate were added to a glass reaction vessel, the mixture was sparged and then placed in a dry box. In each of P12, P13, and P14, DANFABA, Pd-1206, and triethylsilane were added to the reaction vessel, and the reaction vessel was sealed and removed from the drying box. The sparged glacial acetic acid was then added and the mixture was heated to 100 ° C. with stirring for the length of time indicated in the table, then allowed to cool to room temperature. The reaction mixture was purified to remove residual monomer and catalyst. The reaction mixture was added to heptane at P13 and hexane at P14, and the resulting precipitate was collected and dried. The obtained analytical data is shown in the table.

Example P15; P16 and P17
Polymers of TFSNB and C8GAcNB, C10GAcNB or ibornyl EsNB The variables of Examples P15, P16 and P17 are shown in Table G. In a dry box; TFSNB; triethylsilane; toluene; ethyl acetate; Pd-1206; DANFABA and one of C8GAcNB, C10GAcNB or ibornyl EsNB was added to a glass reaction vessel equipped with a stirrer. The reaction vessel was capped and removed from the dry box. Nitrogen sparged glacial acetic acid was added and the mixture was heated to 100 ° C. for the length of time indicated in the table, then allowed to cool to room temperature. After purification to remove residual monomer and catalyst, the reaction mixture was added to heptane and allowed to precipitate, and the precipitate was collected and dried at 90 ° C. under reduced pressure. The obtained analytical data is shown in the table. During purification and separation of the P15 and P16 polymers, some amount of 5-norbornene-2-methanol is produced from the corresponding norbornene acetate, and in the P17 polymer, some amount of norbornene carboxylate is likewise norbornene. Produced from ester. These amounts are given as last numbers in the molar ratios shown in the table below.

Example P18; P19 and P20
Polymers of TFSNB and NBXOCH ₃ , NBCH ₂ OCH ₂ CH ₂ OCH ₃ , or NBC (O) OCH ₂ CH ₂ OH The variables of Examples P18, P19 and P20 are shown in Table H below. A glass reactor equipped with stirring; TFSNB, toluene, ethyl acetate, and _{NBXOCH3, NBCH 2 OCH 2 CH 2} OCH 3, or NBCOOCH ₂ CH ₂ was added one OH. The mixture was sparged with nitrogen for 10 minutes, transferred to a dry box, solid DANFABA, Pd-1206 and triethylsilane were added to the reaction vessel, the reaction vessel was sealed and removed from the dry box. Nitrogen sparged glacial acetic acid was then added and the mixture was heated to 100 ° C. for the length of time indicated in the table, then allowed to cool to room temperature. At P18, THF (2 g) and toluene (4.5 g) were added to the reaction mixture, which was then poured into hexanes (200 g) and precipitated. The precipitate was collected and dried in a 90 ° C. vacuum oven. The obtained analytical data is shown in the table.

Examples P21, P22 and P23
Polymers of TFSNB and NBCH ₂ OCH ₂ CH ₂ CH ₃ , NBC (O) OCH ₂ CH ₂ OC ₂ H ₅ or PPVENB The variables of Examples P21, P22 and P23 are shown in Table J below. At P21 and P22, TFSNB, the appropriate monomer, toluene, and ethyl acetate were added to a glass reaction vessel equipped with a stirrer and the mixture was sparged and placed in a dry box. In P22, TFSNB, PPVENB, toluene and ethyl acetate were added to a glass reaction vessel placed in a dry box. Solid DANFABA, Pd-1206, and triethylsilane were added to the reaction vessel in the dry box, and the reaction vessel was sealed and removed from the dry box. Sparged glacial acetic acid was added and the mixture was heated to 100 ° C. for the length of time indicated in the table. The reaction mixture was left to cool to room temperature. In P21 and P22, THF (2 g) was added to the reaction mixture, then the reaction mixture was poured into hexanes (200 g) and precipitated. At P23, the undiluted reaction mixture was added to hexane and precipitated. The ratio of TFSNB to PPVENB was found to be 84 to 16, and the OD of the polymer was 0.14μ- ¹ . The precipitate or all reactants were collected and dried in a 90 ° C. vacuum oven. The analytical data of the obtained polymer is shown in the table below.

Example P24a-e ECHNB / TFENB / TFSNB
Example P24a-e discloses the synthesis of ECHNB / TFENB / TFSNB polymers with different monomer ratios. The results obtained indicate that CA and SA appear to be a function of the ECHNB concentration in the polymer.

  In 50 mL crimp cap vials, 0.050 moles of monomer containing ECHNB, TFENB, and TFSNB in different proportions (proportions shown in Table K) for each vial were dissolved in toluene (20 g). These solutions were sparged with nitrogen for 10 minutes, sealed, and transferred to a dry box.

The vial was unsealed and Pd-1394 (0.070 g, 0.00005 mol), LiFABA (0.131 g, 0.00015 mol) and triethylsilane (0.116 g, 0.001 mol) were added, respectively. The vials were then resealed, removed from the dry box, and nitrogen sparged glacial acetic acid (0.060 g, 0.001 mol) was added to each solution through the Teflon septum and in an oil bath for 18 hours. The solution was heated to ° C. The vial contents were then allowed to cool to room temperature and 2 g of THF was added to each. The polymer solution was then added to excess n-heptane and allowed to precipitate. The solid polymer was collected and dried in a vacuum oven at 90 ° C. overnight. Table K shows the yield, molecular weight, polydispersity, CA and SA of each polymer.

Examples P25, P26 and P27
ECHNB / TFENB / TFSCH ₂ NB polymer monomer was added to a 50 mL crimp cap vial and dissolved in toluene (20 g). The solution was sparged, sealed and then transferred to the dry box.

To each solution, Pd-1394 (0.070 g, 0.00005 mol), LiFABA (0.131 g, 0.00015 mol), and triethylsilane (0.116 g, 0.001 mol) were added and the vial was resealed, Removed from the dry box. Sparged glacial acetic acid (0.060 g, 0.001 mol) was added through a Teflon septum and the solution was heated to 90 ° C. in an oil bath for about 18 hours. The contents of each vial were allowed to cool to room temperature and 2 g of THF was added. The sample contents were removed and the molecular weight was measured, then the solution was added to excess n-heptane, allowed to settle, the solid collected, dried in a vacuum oven at 90 ° C. overnight, and weighed. Table M shows the yield, molecular weight, polydispersity, CA and SA of each polymer.

Example P28a-g
Polymer of TFENB with monomers shown in Table N This example discloses the synthesis of a polymer containing three monomers with the same feed ratio (30% A, 50% B and 20% TFENB).

  In a 50 mL crimp cap vial, 0.015 mol of monomer A, 0.025 mol of monomer B, and 0.010 mol of TFENB were dissolved in toluene (20 g). These solutions were sparged, then sealed and transferred to a dry box.

To each solution, Pd-1394 (0.070 g, 0.00005 mol), LiFABA (0.131 g, 0.00015 mol), and triethylsilane (0.116 g, 0.001 mol) were added and the vial was resealed, Removed from the dry box. Sparged glacial acetic acid (0.060 g, 0.001 mol) was added to each solution through a Teflon septum and the solution was heated to 90 ° C. in an oil bath for 18 hours. The contents were allowed to cool to room temperature and 2 g of THF was added to each vial. A sample of each vial was removed and measured for molecular weight and polydispersity as shown in Table N. The solution was then added to excess n-heptane, allowed to settle and the solid collected and dried in a vacuum oven at 90 ° C. overnight. The CA and SA of each polymer thin film on a bare silicon wafer were measured and the data obtained are shown in Table N.

The results from Example P28a-g demonstrate that hydrophobicity (indicated by high CA and low SA) can be controlled, at least in part, by changing the structure of the monomers used in the polymerization. It is thought that. That is, (1) the developer-soluble monomer component is changed from TFSNB to TFSCH ₂ NB and TFSCH ₂ CH ₂ NB, thereby increasing the hydrophobicity (see a, b and c); (2) developer-soluble monomer By changing the component from TFSNB to secPrHFAEsNB, the hydrophobicity is increased (see d and e); and (3) The hydrophobicity is increased by changing the acid labile monomer component to HFABOCME or NBCOOBOCME ( a compared with f and d compared with g).

Example P29a-g
Polymer Derived from ECHNB / TFENB / TFSNB Monomer ECHNB / TFENB / TFSNB monomer was polymerized using the feed ratios shown in Table P. The polymerization method used is similar to the method described in Example 24, except that the amount of triethylsilane added is varied to provide different molecular weight polymers.

After separating and drying the solid polymer, each was dissolved in PGMEA and applied onto a bare silicon wafer by spin coating. Each wafer was soft baked at 90 ° C. for 90 seconds, and then the thickness of the film was measured by ellipsometry. Next, each wafer was placed on a spin chuck, covered with 2-butanol, and after 3 seconds, the liquid was removed by spinning. Subsequently, the film was baked at 90 ° C. for 90 seconds, and the thickness was measured again. The resistance of the polymer film to 2-butanol was measured by variation in film thickness. Table P shows the feed ratio, Mw, and thickness variation data after immersion in iso-butanol.

  The results from Example P29a-g are believed to demonstrate that the loss of film thickness (in isobutanol) can be partially adjusted by both the molecular weight and composition of the polymer. That is, in general, the higher the TFENB concentration (or the lower the TFSNB concentration), the less the film thickness loss (compare e and f), and the higher the molecular weight, the same. (Compare e and g).

Example P30a
TFSNB / TFENB / ECHNB / acid NB polymer 3-in a 500 mL reaction vessel equipped with a valve stopper and stirrer, ECHNB (13.02 g, 0.053 mol), TFENB (12.20 g, 0.055 mol), and TFSNB (19 .13 g, 0.075 mol) was dissolved in toluene (77 g). In a 50 mL crimp cap vial, ECHNB (14.73 g, 0.059 mol) and TFENB (5.56 g, 0.025 mol) were dissolved in toluene (11.1 g). Both solutions were sparged and then sealed.

  Pd-1394 (1.394 g, 0.001 mol), LiFABA (2.613 g, 0.003 mol), and triethylsilane (1.16 g, 0.01 mol) were added to the solution in the reaction vessel, and the solution was mixed. did. Glacial acetic acid (0.30 g, 0.005 mol) was added to the solution in the reaction vessel and the solution was heated to 90 ° C. overnight.

  While the reaction vessel is heated, the solution in the crimp cap vial is subjected to a predetermined measurement protocol: (0.065 mL / min for 54 minutes, 0.077 mL / min for 45 minutes, 0.041 mL / min for 84 minutes, 0. 022 mL / min at 155 minutes, 0.012 mL / min at 286 minutes, 0.007 mL / min at 530 minutes, and 0.004 mL / min at 572 minutes).

  After treatment to remove catalyst residue from the polymer, the resulting solution was concentrated using a rotary evaporator and the polymer product was precipitated using excess hexane. The resulting colorless solid polymer (26 g) was dried in a vacuum oven at 90 ° C. overnight, dissolved in 1: 1 THF / MeOH mixture (60 mL), and excess 90:10 MeOH / water. Precipitated. The polymer was dried in a vacuum oven at 90 ° C. overnight to give 23.3 g of polymer (isolated yield, 38%).

¹ H-NMR analysis of the final product did not indicate the presence of residual monomer, and ¹³ C NMR analysis revealed a composition of approximately 35/31/30/4 ECHNB / TFENB / TFSNB / acid NB. When Mw, Mn, and PDI were measured, they were 4300, 2600, and 1.66, respectively. A thin film of this polymer (about 1 micron) spun onto a silicon wafer from a 20% solution in PGMEA had a CA of 77 ° ± 2 °.

Example P30b
Polymer of TFSNB / TFENB / ECHNB / acid NB In the reaction vessel, this polymerization was carried out in the same manner as P30a, except that 0.73 g, 0.0063 mol of triethylsilane was added to the solution, and the following measurement protocol: (0 0.065 mL / min for 54 minutes, 0.077 mL / min for 45 minutes, 0.041 mL / min for 84 minutes, 0.022 mL / min for 155 minutes, 0.012 mL / min for 286 minutes, 0.007 mL / min for 0.007 mL / min 530 minutes and 0.004 mL / min at 978 minutes), the solution in the crimp cap vial was transferred to the reaction vessel under an inert atmosphere.

  40 g of a colorless solid polymer was first obtained, and after reprecipitation, 37.5 g of polymer (isolated yield, 54%) was obtained as was done with P30a.

¹ H-NMR analysis of the final product did not indicate the presence of residual monomer, and ¹³ C NMR analysis revealed a composition of approximately 35/30/30/5 ECHNB / TFENB / TFSNB / acid NB. When Mw, Mn, and PDI were measured, they were 7723, 4350, and 1.78, respectively. A thin film (about 1 micron) of this polymer spun onto a silicon wafer from a 20% solution in PGMEA had a CA of 76 ° ± 1 °.

Example P30b
Polymer of TFSNB / TFENB / ECHNB / acid NB In the reaction vessel, this polymerization was carried out in the same manner as P30a, except that 0.36 g, 0.003 mol of triethylsilane was added to the solution, and a predetermined measurement protocol: (0 0.065 mL / min for 54 minutes, 0.077 mL / min for 45 minutes, 0.041 mL / min for 84 minutes, 0.022 mL / min for 155 minutes, 0.012 mL / min for 286 minutes, 0.007 mL / min for 0.007 mL / min The solution in the crimp cap vial was transferred to the reaction vessel under an inert atmosphere according to 530 minutes and 0.004 mL / min at 632 minutes).

  38 g of the initial polymer was obtained, and 35 g of polymer (separation yield, 50%) was obtained after reprecipitation using excess 85:15 MeOH / water.

¹ H-NMR analysis of the final product did not indicate the presence of residual monomer, and ¹³ C NMR analysis revealed a composition of approximately 35/32/29/4 ECHNB / TFENB / TFSNBB / acid NB. When Mw, Mn, and PDI were measured, they were 12453, 6043, and 2.06, respectively. A thin film (about 1 micron) of this polymer spun onto a silicon wafer from a 20% solution in PGMEA had a CA of 75 ° ± 2 °.

Example P31
ECHNB / TFENB / HFANB / acid NB polymer In a 500 mL reaction vessel equipped with a stirrer in a dry box, ECHNB (74.51 g, 0.300 mol), TFENB (53.34 g, 0.240 mol), and HFANB (16 .45 g, 0.060 mol) was dissolved in toluene (180 g).

  To the solution in the reaction vessel, Pd-1394 (0.8364 g, 0.00060 mol), LiFABA (1.5684 g, 0.0018 mol), and triethylsilane (2.91 g, 0.025 mol) were added, and the solution was stirred. did. Glacial acetic acid (0.72 g, 0.012 mol) was added to the solution followed by heating to 90 ° C. for 40 hours.

  After treatment to remove catalyst residue from the polymer, the resulting solution was concentrated using a rotary evaporator and the polymer product was precipitated with excess 85:15 MeOH / water. The obtained colorless solid polymer (67 g) was dried in a vacuum oven at 90 ° C., dissolved in toluene, and precipitated with excess hexane. The polymer was dried at 90 ° C. overnight in a vacuum oven, yielding 62 g of polymer (separation yield, 43%).

¹ H-NMR analysis of the final product did not show the presence of residual monomer, and ¹³ C NMR analysis revealed a composition of about 46/40/9/5 ECHNB / TFENB / HFANB / acid NB. When Mw, Mn, and PDI were measured, they were 4116, 2478, and 1.66, respectively.

Example P32
TFSNB / NBHFAEsNB / acid NB polymer In a glass reaction vessel equipped with a stirrer, TFSNB (36.7 g, 0.144 mol), NBHFAEsNB (13.3 g, 0.036 mol), toluene (56.0 g), and ethyl acetate (19 0.0 g) was added. The mixture was sparged and then the reaction vessel was placed in a dry box, after which solid DANFABA (0.481 g, 0.0006 mol), Pd-1206 (0.145 g, 0.00012 mol) and triethylsilane (1.465 g , 0.0126 mol) was added to the reaction vessel. The reaction vessel was then removed from the dry box and sparged glacial acetic acid (0.216 g, 0.0036 mol) was added to the reaction mixture. The mixture was then heated to 100 ° C. with stirring for 18 hours. The mixture was allowed to cool to room temperature and then purified to remove residual monomer and catalyst. When Mw, Mn and PDI were measured, they were 5382, 3544 and 1.39, respectively. As noted above, when acid NB was derived from acid dissociable monomers during polymer purification, the polymer composition was found to be 84/14/2 (TFSNB / NBHFAEsNB / acid NB). When CA and SA were measured from the polymer film formed on the substrate, they were 80 ° and 25 °, respectively. The dissolution rate in 0.26N aqueous TMAH was found to be 1601 nm / sec.

Example P33
TFSNB homopolymer TFSNB (44.9 g, 0.176 mol), ethanol (0.811 g, 0.0176 mol), anhydrous toluene (72 mL), and propylene glycol methyl ether (8 mL), 250 mL crimp cap with stir bar Mix in bottle and sparg, then seal bottle. The bottle was placed in a dry box, the seal was broken, and Pd-1206 (849 g, 0.0007 mol), DANFABA (1.69 g, 0.0021 mol), and triethylsilane (1.23 g, 0.0106 mol) were added. The bottle was resealed and the contents were heated to 80 ° C. with stirring in an oil bath for 21 hours. After the mixture was allowed to cool to room temperature, THF (10 g) was added. After treatment to remove catalyst and residual monomer from the resulting solution, it was concentrated using a rotary evaporator and the polymer product was precipitated with excess hexane, collected and dried in a vacuum oven at 90 ° C. Later, 26 g of homopolymer (58%) was obtained. When Mw, Mn, and PDI were measured, they were 5580, 3810, and 1.47, respectively.

Anticipated Example P1p TFSsecPrNB
In a dry box, TFSsecPrNB (10.0 g, 0.0353 mol), triethylsilane (0.286 g, 0.00247 mol), toluene (12 g), ethyl acetate (4 g), Pd-1206 (0.043 g, 0.000035 mol) , And DANFABA (0.084 g, 0.000105 mol) are added to a glass reaction vessel equipped with a stirrer. The reaction mixture is sparged and then the reaction vessel is capped and removed from the dry box. Sparged glacial acetic acid (0.094 g, 0.00157 mol) is added and the reaction mixture is heated to 100 ° C. for 15-20 hours and allowed to cool to room temperature. After purification to remove residual monomer and catalyst, the polymer is precipitated by adding excess hexane to the reaction mixture. After collection and drying, the solid is the target polymer.

Lithographic behavior of TFSNB homopolymer as topcoat layer Example TC-1
A 2.5 wt% solution of TFSNB homopolymer in 2-methyl-1-propyl alcohol was prepared. The homopolymer has a Mw of 19400 in solution 1, an Mw of 8500 in solution 2, and an Mw of 5300 in solution 3. Such homopolymers can be prepared, for example, by the method of Example P33, but the amount of triethylsilane and / or the reaction time can be varied to achieve different molecular weights. Each solution is applied to a substrate to form a protective film having a thickness of about 300 nm.

Each of the three coated substrates was contacted with a 2.38 wt% aqueous solution of TMAH (0.26N) for 60 seconds and its solubility in alkaline developer was evaluated. Evaluation was carried out by measuring the variation of the thickness of the protective film before and after contact with the alkaline developer. The results are shown in Table R1 below.

  From the results of Table S, it is understood that the protective film-forming substance of the present invention has good solubility in an alkali developer and can be used as an alkali-soluble protective film.

Example TC-2
Water that can be used as a liquid for immersion lithography for three additional coated substrates prepared by the method of Example TC-1, except that the thickness of the coated film is as shown in Table R2. Was tested for resistance. Evaluation was carried out by measuring the variation of the thickness of the protective film before and after contact with water. The results are shown in Table R2 below.

  From the results of Table R2, it is understood that the protective film-forming substance of the present invention has good resistance to water and can be used as a protective film in immersion lithography.

Example TC-3
The organic antireflection film composition ARC29 (Brewer Science, Inc.) was applied to a silicon wafer using a spinner, baked, and dried on a hot plate at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 77 nm. did. A positive photoresist composition is applied to TAF-P6111 (Tokyo Ohka Kogyo Co., Ltd.) on an antireflection film, pre-baked, dried on a hot plate at 130 ° C. for 90 seconds, and 150 nm on the antireflection film. A photoresist film having a thickness of 5 mm was formed.

  The protective film-forming substance used in Example TC-1 was applied to a photoresist film and heated at 90 ° C. for 60 seconds to form a protective film having a thickness of about 70 nm.

  The sample was then tested for two-beam interference using a immersion lithography laboratory kit (LEIES 193-1 from Nikon Corp.). This was then subjected to PEB treatment at 115 ° C. for 90 seconds, followed by development with a 2.38 wt% aqueous solution of TMAH at 23 ° C. for 60 seconds. In this development step, the protective film was completely removed, and the developability of the photoresist film was good.

  When the thus obtained line-and-space pattern having a 65 nm pitch was observed using a scanning electron microscope (SEM), the pattern shape was good.

Example TC-4
The organic antireflection film composition ARC29 (Brewer Science, Inc.) was applied to a silicon wafer using a spinner, baked, and dried on a hot plate at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 77 nm. did. A positive photoresist composition, TArF-P6111 (Tokyo Ohka Kogyo Co., Ltd.) was applied to an antireflection film, pre-baked, dried on a hot plate at 130 ° C. for 90 seconds, and 170 nm on the antireflection film. A photoresist film having a thickness of 5 mm was formed.

  A protective film-forming substance using Example TC-1 was applied to a photoresist film and heated at 90 ° C. for 60 seconds to form a protective film having a thickness of about 70 nm.

  Pure water is dropped on a substrate having a protective film formed thereon, and then an exposure apparatus (Nikon Corp.'s NSR-S302) is used to expose it to light of a 193 nm ArF excimer laser. Further, pure water was dripped there for 60 seconds. Next, this was subjected to PEB treatment at 115 ° C. for 90 seconds, followed by development with a 2.38 wt% aqueous solution of TMAH at 23 ° C. for 60 seconds.

  When the number of defects in the line-and-space pattern (1: 1) having a pitch of 130 nm obtained in this way was measured using KLA2351 (KLA Tencor Co., Ltd.), it was formed there. It was reduced to 0.5% of the number of defects in the comparative sample having no protective film.

Lithographic behavior of TFSNB copolymer as topcoat layer Example TC-5a-f
Using the TFSNB copolymer shown in Table S, the measurement method 2 described above, contact angle (CA), falling angle (SA), dissolution rate (DR) in aqueous alkaline developer and water resistance (WP). Was measured. The data presented show that the film formed from such a sample has a contact angle and tumbling indicating that such a material is suitable for use as a protective film (topcoat) in an immersion lithography process. Angle, water resistance, and dissolution rate were shown. In addition, evaluation of such films for scan capability also gave acceptable results.

  In addition to the evaluation of the copolymer, a first mode coated silicon wafer was prepared by applying the following film-forming material to the wafer by spin coating. In each wafer, first, an organic antireflection film composition “ARC29” (Brewer Science, Inc.) was applied to the wafer, baked, and dried on a hot plate at 225 ° C. for 60 seconds to have an antireflection thickness of about 77 nm. A film was formed. Next, a positive photoresist composition of “TARF-P6111ME” (Tokyo Ohka Kogyo Co., Ltd.) was applied to an antireflection film, pre-baked, dried on a hot plate at 130 ° C. for 90 seconds, A photoresist film having a thickness of 225 nm was formed. The composition of each copolymer from Table S was then applied to one of the coated wafers on a photoresist film and heated at 90 ° C. for 60 seconds to form a protective film or topcoat layer having a thickness of about 140 nm. .

  Next, using a “NSR S302A” (Nikon Corp.) lithography tool equipped with a 193 nm ArF excimer laser source, each coated wafer was subjected to normal dry exposure through a mask pattern. After the exposure, pure water at 23 ° C. was dropped onto the protective film for 1 minute while the substrate was continuously rotated by a spinner chuck to simulate an immersion lithography environment. After adding pure water to the substrate, the substrate was subjected to PEB treatment at 130 ° C. for 90 seconds, and then subjected to an alkaline developer (0.26N TMAH aqueous solution) at 23 ° C. for 60 seconds during the pattern development process. . As a result of this development process, the topcoat layer was completely removed, and a well-developed pattern was formed on the resist film. In such a pattern, a line-and-space (1: 1) resist pattern having a pitch of 130 nm was observed using a scanning electron microscope (SEM), and the pattern shape was a good rectangle.

  Continuing the evaluation of the copolymer of Table S, a second mode coated silicon wafer was prepared as described above for the first mode. However, the second type wafer is exposed using an immersion lithography laboratory kit (Nikon Corp. LEIES 193-1), where LEIES is used, and a 193 nm ArF excimer laser source is used for each. The wafer was set against two-beam interference.

  After exposure, each wafer was subjected to the development process used for the first method. In this development process, the topcoat layer was completely removed, and a well-developed pattern appeared on the resist film. In such a pattern, a line-and-space (1: 1) resist pattern with a pitch of 130 nm was observed using SEM and found to have a good pattern shape of a good rectangle.

Immersion Exposure Evaluation of Compositions P30a-c and P31 Using the polymers of Examples P30a-c and P31, developable polymer compositions were prepared according to Table T below:

  An organic antireflective coating material (Brewer Science, product ARC-29A) was applied to an 8-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a 77 nm film. Wafers and films were used as substrates. Each polymer composition was uniformly applied to the substrate using a spinner, pre-baked at 110 ° C. for 90 seconds on a hot plate, and dried to form a developing polymer layer having a thickness of about 130 nm.

  Next, an immersion two-beam interferometer exposure was performed using a LEIES 193-1 two-beam interferometer (manufactured by Nikon) for immersion exposure, using a prism, water, and two 193 nm interferometers. This method is reported in Journal of Vacuum Science & Technology B (US) (19: 6 2001, p. 2353-2356) and is useful in laboratories to obtain line-and-space (L & S) patterns. It is publicly known as a method.

  The substrate was then subjected to post exposure bake (PEB) at 100 ° C. for 90 seconds, followed by paddle development for 60 seconds at 2.38 wt% aqueous trimethylammonium hydroxide (TMAH) at 23 ° C., followed by After rinsing with pure water for 30 seconds, spin drying was performed to obtain 1: 1 as a resist pattern (the following “L / S pattern”).

  When the L / S pattern of each sample was observed using a scanning electron microscope (SEM), a 1: 1 resist pattern was generated at 65 nm line-and-space. Furthermore, regarding the form of the resist pattern, the line showed no waveform and almost no roughness.

Comparative Example As part of the immersion exposure evaluation described above, a pattern formed using the composition made from the polymer of Example P30a-c was replaced with an alternative composition formed using the polymer of Example P31. Compared to the pattern of objects.

  When an L / S pattern obtained using the alternative composition by the same exposure method was observed using SEM, a 65 nm line-and-space was formed in a 1: 1 resist pattern. However, the resist pattern form had noticeable unevenness and considerable roughness on the line.

Film Resistance to Alcohol Two wafers were coated with the polymer compositions of Examples 30b and 30c by the method described so far and the thickness of each film was measured. Next, after the temperature of the substrate was lowered to room temperature, isobutanol was dropped from the nozzle, the thickness of the resist film was measured again, and then placed in a rotary dryer. The loss in the case of the resist of Example 2 was 12.7 nm, and in the case of Example 3, it was 9.2 nm.

  However, when the same alcohol tolerance test was performed on wafers coated with the alternative composition, a loss of 20.2 nm was observed.

  Similar results are expected with other alcohols such as 4-methyl-2-pentanol.

  As is apparent from the above results, the polymer composition produced using the polymer of Example 30a-c resulted in a film provided with a high resolution resist pattern as a result of immersion exposure. Even better results were obtained with little film loss in the alcohol resistance test. Furthermore, when a topcoat film was formed from the polymer composition using an alcohol solvent, good results were obtained in that no mixed layer was formed between the resist layer and the topcoat film layer.

  In contrast, the pattern obtained by immersion exposure of the alternative composition was not good, and the alcohol resistance test resulted in considerable loss of the film.

  Furthermore, the films formed from the compositions using the polymers of Example P30a-c are each found to have high water repellency, i.e. high hydrophobicity, without the use of a protective film. When used as a photoresist for immersion lithography, good results were obtained in that the immersion liquid (for example, water) was hardly dissolved from the resist film.

  Examples, data and discussion thereof, and through them, topcoat polymers, topcoat (protective film forming) materials formed using such polymers, topcoat layers formed thereby, and such It can be seen that the embodiment of the process using layers provides a solution to the above-mentioned problems found in previously known materials. Such topcoat materials and the layers formed thereby allow alkali solubility, resistance to immersion liquid, low solubility to or with photoresist layer components, from and / or photoresist layers of such photoresist layers. Provides good protection against oozing, good protection as a gas barrier layer, and low optical density. Furthermore, the topcoat material and the layers formed thereby have better scanning capabilities and reduced defects during the immersion lithography process compared to processes where no such topcoat layer is used. . Furthermore, the layers exhibit high contact and receding angles and low tumbling angles that are considered desirable for such performance. It will also be appreciated that the examples provided herein are illustrative rather than limiting and may be obtained through the polymer design process. For example, a non-self-developing polymer film of TFSNB and NBXOH (97: 3) has a CA of 70 °, an SA of 22 °, a dissolution rate (DR) of 1710 nm / sec, and a water resistance of − 2%. Similar to the non-self-developed version disclosed in Example TC5a-f, this polymer also showed advantageous results after both wet and dry exposure development tests described in such examples.

  In addition, such data and discussion thereof includes developing polymers, developing materials formed by such polymers (photoresists), developing layers formed thereby (photoresist layers or films), and such layers. It has been demonstrated that embodiments of processes that use can provide solutions to the problems described above, or can be utilized with these topcoat materials and layers to provide such solutions. is doing. Such photoresist materials and films formed therefrom exhibit good resistance to immersion fluids and have little or no interaction with the topcoat embodiments described above during the immersion lithography process, and It has also been shown that the scanning capability is superior and defects are reduced compared to processes where alternative photoresist materials are used. In addition, the layers exhibit high contact and receding angles and low tumbling angles that are considered desirable for such performance.

  Although the invention has been described with reference to various embodiments and examples, it should be understood that variations thereof will be apparent to those skilled in the art upon reading this specification. Accordingly, it is understood that any such modifications fall within the scope and spirit of the embodiments of the invention and fall within the scope of the appended claims.

FIG. 1 shows an immersion lithography system representing a lens element having a movement in the direction of an arrow, a resist layer, a fluid between the resist layer and the lens element (immersion medium), and a non-retaining immersion fluid covering a part of the resist layer Indicates. FIG. 2 shows the contact angle, tumbling angle and receding angle for the droplet covering the surface.

Claims (71)

A non-self-developing polymer consisting of norbornene-type repeating units having the formula I:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a -QNHSO ₂ R ⁵ group (where Q is 1 to 5). A linear or branched alkyl spacer of carbon, and R ⁵ is a perhalo group of 1 to 10 carbon atoms)]
A non-self-developed polymer comprising a first norbornene-type repeating unit represented by Formula II:
[Wherein X and n are as defined for formula I, and R ⁶ to R ⁹ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ⁶ to R ⁹ is —Q ^‡ (CO) O— (CH ₂ ) _m —R ¹⁰ (where Q ^‡ is optional, A linear or branched alkyl spacer of 5 carbons, m is an integer of 0 or 1-3, and R ¹⁰ is a linear or branched perhaloalkyl of 1 to 10 carbon atoms) Is]
The non-self-developing polymer according to claim 1, further comprising a second type of norbornene-type repeating unit represented by: The non-self-developing polymer according to claim 2, wherein R ⁵ is CF ₃ and R ¹⁰ is C ₂ F ₃ . Q is independently a CH ₂ or _CH 2 CH _2, non-self imageable polymer of claim 3.   The non-self-developing polymer according to claim 2, 3 or 4, wherein the molar ratio of the first repeating unit to the second repeating unit is 99: 1 to 60:40.   The non-self-developing polymer according to claim 5, wherein the molar ratio of the first repeating unit to the second repeating unit is 95: 5-75: 25.   The non-self-developing polymer according to claim 2, 3 or 4, having a molecular weight (Mw) of 2000 to 10,000.   The non-self-developing polymer according to claim 7, having a molecular weight (Mw) of 4000 to 7000. Having a molecular weight (Mw) of 4000-6000, a polydispersity of less than 2, a molar ratio of the first and second repeat units of 85: 15-75: 25, R ⁵ is CF ₃ , R ¹⁰ The non-self-developing polymer according to claim ₂ , wherein is C ₂ F ₅ , Q is CH ₂ and Q ^‡ is absent. Formula III:
[Wherein X and n are as defined for formula I and R ¹¹ to R ¹⁴ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹¹ to R ¹⁴ is represented by the following formula:
(Wherein m is an integer from 1 to 3, Q ^‡ is as defined in claim 2 and Q ^* is a linear or branched alkyl spacer of 1 to 5 carbons)
Is one of the A, B or C groups of
The non-self-developing polymer according to claim 1, further comprising a third type of norbornene-type repeating unit represented by: Formula IV:
[Wherein X and n are as defined for formula I and R ¹⁵ to R ¹⁸ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹⁵ to R ¹⁸ is represented by the following formula:
(In the above formula, each X is independently F or H, q is each independently an integer of 1 to 3, p is an integer of 1 to 5, and Q ^* is 1 to 5 carbon atoms. A linear or branched alkyl spacer, Z is a linear or branched halo or perhalo spacer of 2 to 10 carbons)
One of the D, E or F groups of
The non-self-developing polymer according to claim 1 or 2, further comprising a fourth type of norbornene-type repeating unit represented by:   40-98 mol% (mol%) of the first type of repeating units and, independently, about 1-30 mol% of the second type of repeating units, and about 1-40 mol% A third type of repeating unit and a fourth type of repeating unit, provided that if a second type of repeating unit is present, either a third repeating unit or a fourth repeating unit is also present. The non-self-developing polymer according to claim 10 or 11.   50 to 80 mol% of the first type of repeating unit, and independently, if present, about 10 to 25 mol% of the second type of repeating unit and about 5 to 30 mol% of the third type of repeating unit. 11. A type of repeating unit and a fourth type of repeating unit, provided that when a second type of repeating unit is present, one of the third repeating unit or the fourth repeating unit is also present. Or the non-self-developing polymer according to 11;   The non-substituted according to any one of claims 1, 2, 10 and 11, further comprising a 5-substituted linear or branched alkyl norbornene repeating unit or a 5-substituted linear or branched alkyl ester norbornene. Self-developing polymer.   15. The 5-substituted linear or branched alkyl norbornene repeating unit or 5-substituted alkyl ester repeating unit is hexyl or butyl 5-substituted norbornene repeating unit or 5-substituted isobornyl ester norbornene. Non-self-developed polymer.   The non-self-developing polymer according to claim 12 or 13, having a molecular weight (Mw) of 2000 to 10,000.   The non-self-developing polymer of claim 16, having a molecular weight (Mw) of 3500 to 7000. 60 to 85 mol% of the first repeating unit and 15 to 40 mol% of the second repeating unit, in which each n is 0, R ⁵ is CF ₃ , R ¹⁰ is C ₂ F ₃ , Q is The non-self-developing polymer according to claim ₂ , wherein CH ₂ , m is 1, and Q ^‡ is not present.   19. The non-self of claim 18, comprising 75-85 mol% first repeat unit and 15-25 mol% second repeat unit and having a molecular weight (Mw) of 3000-6000 with a polydispersity of less than 2. Developable polymer. Formula IA:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a -QNHSO ₂ R ⁵ group (where Q is 1 to 5). A linear or branched alkyl spacer of carbon, R ⁵ is a perhalo group of 1 to 10 carbon atoms)]
A first norbornene-type monomer represented by:
Optionally charging one or more other norbornene-type monomers structurally different from the first monomer into the reaction vessel;
Add further appropriate solvent, catalyst and optional cocatalyst to the reaction vessel;
Stirring the contents of the reaction vessel to dissolve the first monomer, any other monomer, catalyst, and optional cocatalyst in a solvent;
Imparting heat and continuous stirring to the contents for a time sufficient to polymerize the first monomer present therein and any other monomers;
A process for producing a non-self-developing polymer comprising norbornene-type repeating units. Optional charging to the reaction vessel is of formula IIA:
[Wherein X and n are as defined for formula I and R ⁶ to R ⁹ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group, provided that at least one of R ⁶ to R ⁹ is —Q ^‡ (CO) O— (CH ₂ ) _m —R ¹⁰ (where Q ^‡ is optional and 1 to A linear or branched alkyl spacer of 5 carbons, m is an integer of 0 or 1-3; R ¹⁰ is a linear or branched perhaloalkyl of 1 to 10 carbon atoms) Is]
21. The method according to claim 20, comprising charging a norbornene type monomer represented by the formula: Optional charging to the reaction vessel is of formula IIA:
[Wherein X and n are as defined for formula IA, and R ⁶ to R ⁹ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group, provided that at least one of R ⁶ to R ⁹ is —Q ^‡ (CO) O— (CH ₂ ) _m —R ¹⁰ (where Q ^‡ is optional, and 1 to 5 when present) A linear or branched alkyl spacer of carbon, where m is an integer of 0 or 1-3; R ¹⁰ is a linear or branched perhaloalkyl of 1 to 10 carbon atoms). is there]
And a norbornene-type monomer represented by formula IIIA:
[Wherein X and n are as defined for formula IA and R ¹¹ to R ¹⁴ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹¹ to R ¹⁴ is represented by the following formula:
(Wherein m is an integer from 1 to 3, Q ^‡ is as defined above, Q ^* is a linear or branched alkyl spacer of 1 to 5 carbons)
One of the A, B or C groups]; and / or the formula IVA:
[Wherein X and n are as defined for formula I and R ¹⁵ to R ¹⁸ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹⁵ to R ¹⁸ is represented by the following formula:
(In the above formula, each X is independently F or H, q is each independently an integer of 1 to 3, p is an integer of 1 to 5, and Q ^* is 1 to 5 carbon atoms. A linear or branched alkyl spacer, Z is a linear or branched halo or perhalo spacer of 2 to 10 carbons)
One of the D, E or F groups of
21. The method according to claim 20, comprising charging one or a plurality of norbornene-type monomers represented by:   One or more optionally introduced norbornene type monomers represented by the formula IIIA and / or IVA are a 5-position substituted linear or branched alkyl norbornene type monomer and a 5-position substituted linear or branched alkyl. The method of claim 22 further comprising an ester norbornene-type monomer. Further charging into the reaction vessel
A solvent selected from the group of benzene, toluene, xylene, hexane, heptane, cyclohexane, dichloromethane, ethyl chloride, tetrahydrofuran, ethyl acetate and mixtures thereof;
Any cocatalyst selected from tetrakis (pentafluorophenyl) borate lithium-diethyl ether complex (LiFABA) and N-dimethylaniline-tetrakis- (pentafluorophenyl) borate (DANFABA);
Bis (triisopropylphosphine) acetic acid palladium-acetonitrile complex tetrakis (pentafluorophenyl) borate (Pd1206) and bis (tricyclohexyl-t-butylphosphine) acetic acid palladium-acetonitrile complex tetrakis (pentafluorophenyl) borate 24. A process according to any one of claims 20, 21, 22 or 23 comprising charging a catalyst selected from (Pd1394) into a reaction vessel.   A top coat composition comprising one or a plurality of norbornene-type repeating units, wherein at least one of the repeating units imparts alkali solubility to the polymer, and a solvent. At least one of the repeating units is of formula I:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a linear or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a -QNHSO ₂ R ⁵ group (where Q is 1 to 5). A linear or branched alkyl spacer of carbon, R ⁵ is a perhalo group of 1 to 10 carbon atoms); and / or Formula III:
[Wherein X and n are as defined for formula I, and R ¹¹ to R ¹⁴ are each independently hydrogen, a linear or branched alkyl group, or linear or branched. A haloalkyl group wherein at least one of R ¹¹ to R ¹⁴ is represented by the following formula:
(Wherein m is an integer from 1 to 3, Q ^‡ is as defined in claim 2 and Q ^* is a linear or branched alkyl spacer of 1 to 5 carbons)
Is one of the A, B or C groups of
The topcoat composition according to claim 25, represented by:   27. The topcoat composition of claim 25 or 26, wherein the one or more norbornene-type repeat units of the non-self-developed polymer further comprise one or more types of repeat units that provide polymer hydrophobicity control. One or more types of repeating units that provide hydrophobicity control to the polymer are represented by Formula II:
[Wherein X and n are as defined for formula I, and R ⁶ to R ⁹ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. Represents a branched haloalkyl group, provided that at least one of R ⁶ to R ⁹ is —Q ^‡ (CO) O— (CH ₂ ) _m —R ¹⁰ (where Q ^‡ is optional and present) Is a linear or branched alkyl spacer of 1 to 5 carbons, m is an integer of 0 or 1 to 3; R ¹⁰ is a linear or branched perhaloalkyl of 1 to 10 carbon atoms And / or Formula IV:
[Wherein X and n are as defined for formula I and R ¹⁵ to R ¹⁸ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹⁵ to R ¹⁸ is represented by the following formula:
(In the above formula, each X is independently F or H, q is each independently an integer of 1 to 3, p is an integer of 1 to 5, and Q ^* is 1 to 5 carbon atoms. A linear or branched alkyl spacer, Z is a linear or branched halo or perhalo spacer of 2 to 10 carbons)
One of the D, E or F groups of
28. A topcoat composition according to claim 27, selected from repeating units of the type represented by:   29. A topcoat composition according to any one of claims 25 to 28, optionally containing one or more crosslinking agents, acidic substances or surfactants.   A topcoat composition comprising the non-self-developing polymer according to any one of claims 1 to 19 and a solvent, optionally containing one or more crosslinking agents, acidic substances or surfactants. Solvents are n-butyl alcohol, isobutyl alcohol, n-pentanol, 4-methyl-2-pentanol, 2-octanol, 2-perfluorobutylethanol (C ₄ F ₉ CH ₂ CH ₂ OH), perfluoropropylmethanol ( _{(C 3 F 7) (CH} 2 OH)), H (CF 2) 2 CH 2 -O- (CF 2) 2 -H, H (CF 2) 7 - (CO) O-CH 3, and H ( _{CF 2) 4 - (CO)} O-C 2 H 5, and is selected from the group consisting of a mixture thereof, the topcoat composition of claim 30. A developable polymer composed of norbornene-type repeating units having the formula I:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a -QNHSO ₂ R ⁵ group (where Q is 1 to 5). A linear or branched alkyl spacer of carbon, R ⁵ is a perhalo group of 1 to 10 carbon atoms)]
A first norbornene-type repeating unit represented by:
Formula V:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to ^5; the ^{R 19 R 22} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹⁹ to R ^{22 is} a group represented by formula G:
Wherein Q ^‡ is optional and, if present, is a 1-5 carbon linear or branched alkyl spacer]
A second norbornene-type repeating unit represented by:
Formula VI:
[Wherein X and n are as defined for formula V, and R ²³ to R ²⁶ each independently represent hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ²³ to R ²⁶ is represented by the formula:
(Wherein Q ^‡ is as defined above and R ²⁷ is a linear or branched alkyl group of 1 to about 5 carbon atoms)
Is a group represented by one of
A third norbornene-type repeating unit represented by:
A polymer comprising The following formula V (acid):
[In the formula VI acid, X, n and R ²³ to R ²⁶ are as defined for formula VI of claim 30 provided that at least one of R ²³ to R ²⁶ is a Q ^‡ -COOH group. (Where Q ^‡ is as defined for Formula VI of claim 32)]
31. The developable polymer of claim 30, further comprising a fourth type of repeating unit represented by:   The developable polymer according to claim 32 or 33, wherein in the repeating unit represented by the formula I, Q is a linear alkyl group having 1 to 3 carbon atoms. In repeating unit represented by the formula I, Q is CH _2, ^{R 5} is CF _3, imageable polymer of claim 34. Some or all of the repeating units of formula I may have the following formula VII:
[Wherein Q ^‡ is as defined in claim 32]
36. The developable polymer of claim 35, wherein the developable polymer is replaced with a repeating unit represented by: In repeating unit represented by the formula ^VI, one of the ^{R 23 R 26 is,} in ^{R 27} is 1 or 2 carbons, an H radical or is CH ₂ no Q ^‡, claim 35 Development type polymer. In repeating unit represented by the formula ^VI, one of the ^{R 23 R 26 is,} in ^{R 27} is 1 or 2 carbons, an J group which is or CH ₂ no Q ^‡, claim 35 Development type polymer. In repeating unit represented by the formula ^VI, one of the ^{R 23 R 26 is,} in ^{R 27} is 1 or 2 carbons, K group or is CH ₂ no Q ^‡, claim 35 Development type polymer.   33. Each of the first type and the second type of repeating units is independently contained in an amount of 1 to 50 mol% and the third type of repeating units is independently contained in an amount of 20 to 80 mol%. The developable polymer described in 1.   30 to 70 mol% of a third type of repeating unit, 10 to 40 mol% of a first type of repeating unit, and 5 to 30 mol% of a second type of repeating unit. Item 41. The developable polymer according to Item 40.   34. The developable polymer of claim 33 comprising 20 to 80 mol% of a third type of repeating unit and a fourth type of repeating unit and 1 to 50 mol% of a second type of repeating unit.   43. The fourth type of repeat unit is derived from a third type of repeat unit and is 5-30 mol% of the sum of the third type of repeat unit and the fourth type of repeat unit. Development type polymer.   44. The developable polymer according to any one of claims 40 to 43, having a molecular weight (Mw) of 2000 to 10,000.   45. The developable polymer of claim 44, having a Mw of 3500 to 7000. A total of 45 to 65 mol% of the third and fourth repeating units, 5 to 25 mol% of the second repeating unit, and 25 to 35 mol% of the first repeating unit; N is 0, Q is CH ₂ and R ⁵ is CF ₃ ; in the second repeating unit, n is 0, Q ^‡ is not present, and n is 0 in the third repeating unit. , R ²³ to R ²⁶ are the group (H) in which R ²⁷ is CH ₂ CH ₃ and the other R ²³ to R ²⁶ are hydrogen, and the amount of the fourth type of repeating unit is the third 34. The developable polymer of claim 33, which is 10-25% of the sum of the type repeating unit and the fourth type repeating unit.   47. The developable polymer of claim 46, having a molecular weight (Mw) of 3500-6500 and a polydispersity of less than 2. Formula IA:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a -QNHSO ₂ R ⁵ group (where Q is 1 to 5). A linear or branched alkyl spacer of carbon, R ⁵ is a perhalo group of 1 to 10 carbon atoms)]
A first norbornene-type monomer represented by:
Formula VA:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to ^5; the ^{R 19 R 22} are each independently hydrogen, straight Represents a chain or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹⁹ to R ²² is represented by the following formula:
Wherein Q ^‡ is optional and, if present, is a linear or branched alkyl spacer of 1 to 5 carbons]
A second norbornene-type repeating unit represented by:
Formula VIA:
[Wherein X, n and R ²³ to R ²⁶ are as defined for formula I, wherein at least one of R ²³ to R ²⁶ has the following formula:
(Wherein Q ^‡ is as defined above and R ²⁷ is a linear or branched alkyl group of 1 to about 5 carbon atoms)
Is a group represented by
A third norbornene-type repeating unit represented by:
Into the reaction vessel;
Add further appropriate solvent, catalyst and optional cocatalyst to the reaction vessel;
Stirring the contents of the reaction vessel to dissolve the first monomer, any other monomer, catalyst, and optional cocatalyst in a solvent;
Imparting heat and continuous stirring to the contents for a time sufficient to polymerize the monomers therein;
A process for producing a developable polymer comprising norbornene-type repeating units. Further charging into the reaction vessel
A solvent selected from the group of benzene, toluene, xylene, hexane, heptane, cyclohexane, dichloromethane, ethyl chloride, tetrahydrofuran, ethyl acetate and mixtures thereof;
Any cocatalyst selected from tetrakis (pentafluorophenyl) borate lithium-diethyl ether complex (LiFABA) and N-dimethylaniline-tetrakis- (pentafluorophenyl) borate (DANFABA);
Bis (triisopropylphosphine) acetic acid palladium-acetonitrile complex tetrakis (pentafluorophenyl) borate (Pd1206) and bis (tricyclohexyl-t-butylphosphine) acetic acid palladium-acetonitrile complex tetrakis (pentafluorophenyl) borate 49. The method of claim 48, comprising charging a catalyst selected from (Pd1394) into a reaction vessel.   Heating the contents of the reaction vessel to a temperature selected from the range of 60 ° C. to 100 ° C., and maintaining the contents at that temperature for up to 24 hours or until the polymerization reaction is complete 50. The method of claim 48 or 49, comprising: It consists of one or more types of norbornene-type repeating units, wherein at least one type of repeating units is of formula I:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to 5; ^{R 1} from ^{R 4} are each independently hydrogen, straight Represents a linear or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹ to R ⁴ is a —QNHSO ₂ R ⁵ group (where Q is 1 to A linear or branched alkyl spacer of ⁵ carbons, and R ⁵ is a perhalo group of 1 to 10 carbon atoms)]
A developing composition comprising a developing polymer in which at least another type of the repeating unit has an acid labile pendant group, a solvent, and a photoacid generator. One or more types of norbornene-type repeating units are represented by the formula V:
[In the formula, X is _{-CH 2 -, - CH 2 -CH} 2 -, O or S; n is an integer from 0 to ^5; the ^{R 19 R 22} are each independently hydrogen, straight Represents a linear or branched alkyl group, or a linear or branched haloalkyl group, provided that at least one of R ¹⁹ to R ²² is represented by the following formula G:
Wherein Q ^‡ is optional and, if present, is a 1-5 carbon linear or branched alkyl spacer]
The developing composition of claim 51, further comprising a second norbornene-type repeating unit represented by: A repeating unit of the type having an acid labile pendant group is of formula VI:
[In the formula VI; X and n are as defined for the formula V, and R ²³ to R ²⁶ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ²³ to R ²⁶ is represented by the formula:
(Wherein Q ^‡ is as defined above and R ²⁷ is a linear or branched alkyl group of 1 to about 5 carbon atoms)
Is a group represented by one of
53. The developing composition according to claim 51 or 52, represented by:   54. A developable composition according to any one of claims 51 to 53, wherein the one or more types of norbornene-type repeat units further comprise a repeat unit type for controlling the hydrophobicity of the developable polymer. The repeating unit type for controlling the hydrophobicity of the polymer is represented by the following formula II:
[Wherein X and n are as defined for formula I, and R ⁶ to R ⁹ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ⁶ to R ⁹ is —Q ^‡ (CO) O— (CH ₂ ) _m —R ¹⁰ (where Q ^‡ is optional, Any linear or branched alkyl spacer of 5 carbons, m is an integer of 0 or 1-3; R ¹⁰ is a linear or branched perhaloalkyl of 1 to 10 carbon atoms. And / or the following formula IV:
[Wherein X and n are as defined for formula I and R ¹⁵ to R ¹⁸ are each independently hydrogen, a linear or branched alkyl group, or a linear or branched group. A haloalkyl group wherein at least one of R ¹⁵ to R ¹⁸ is represented by the following formula:
(In the above formula, each X is independently F or H, q is each independently an integer of 1 to 3, p is an integer of 1 to 5, and Q ^* is 1 to 5 carbon atoms. A linear or branched alkyl spacer, Z is a linear or branched halo or perhalo spacer of 2 to 10 carbons)
One of the D, E or F groups of
55. The developable composition of claim 54, selected from repeating units of the type represented by:   56. The developing composition according to any one of claims 51 to 55, wherein the solvent contains at least one of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) together with γ-butyrolactone (GBL).   The photoacid generator is (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, (4-methoxyphenyl) ) Diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, bis (p-tert-butylphenyl) iodonium nonafluorobutanesulfonate 6. One or more compounds selected from the group consisting of triphenylsulfonium nonafluorobutane sulfonate, and diphenyl iodonium trifluoromethane phosphate. Developing composition according to any one of 56.   The method further comprising any amine moiety selected from the group consisting of trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine and mixtures thereof. The developing composition according to any one of 51 to 57.   A developing composition comprising the developing polymer according to any one of claims 30 to 45, a solvent, and a photoacid generator (PAG).   60. The developing composition according to claim 59, wherein the solvent comprises at least one of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) together with γ-butyrolactone (GBL).   PAG is (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, (4-methoxyphenyl) diphenylsulfonium Trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, bis (p-tert-butylphenyl) iodonium nonafluorobutanesulfonate, triphenyl 60. Also comprising one or more compounds selected from the group consisting of sulfonium nonafluorobutane sulfonate and diphenyl iodonium trifluoromethane phosphate Developing composition as claimed in 60.   The method further comprising any amine moiety selected from the group consisting of trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine and mixtures thereof. 62. The developing composition according to any one of 59 to 61. First, a photoresist composition is applied onto a substrate to form the photoresist layer;
Second, the topcoat composition according to any one of claims 25 to 31 is applied on a substrate to form a protective layer covering the photoresist layer;
Imagewise exposing the photoresist layer through the protective layer using an immersion lithography exposure tool that provides immersion fluid to at least a portion of the protective layer;
Developing the pattern in the photoresist layer with an aqueous alkaline developer solution, the solution removing the protective layer during development;
An immersion lithography method comprising:   64. The method of claim 63, wherein the photoresist composition is a developable composition according to any one of claims 51 to 62.   65. A method according to claim 63 or 64, wherein the substrate is first fired prior to the second application.   66. A method according to any one of claims 63 to 65, wherein the substrate is subjected to a second baking prior to imagewise exposure.   67. A method according to any one of claims 63 to 66, wherein the substrate is subjected to a third baking prior to development.   68. A method according to any one of claims 63 to 67, wherein any calcination is performed at a temperature of about 70 <0> C to about 140 <0> C for about 40 to about 120 seconds.   69. The method according to any one of claims 63 to 68, wherein the alkaline developing aqueous solution is a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).   70. The method of claim 69, wherein the TMAH solution is 0.26N.   The application of heat comprises heating the contents of the reaction vessel to a temperature selected from the range of 60 ° C. to 100 ° C. and maintaining the contents at that temperature within 24 hours or until the polymerization reaction is complete. Item 21. The method according to Item 20.